Groups i and ii metal containing micellar complexes

ABSTRACT

SOLID, GROUPS I AND II METAL-CONTAINING MICELLAR COMPLEXES ARE PREPARED BY ISOLATING THE SOLID, METAL-CONTAINING MATTER FROM HOMOGENIZED, OVERBASED ORGANIC ACIDS WITH THE AID OF SUCH CONVERSION AGENTS AS ALIPHATIC CARBOXYLIC ACIDS, WATER, ALCOHOLS, PHENOLS, KETONES, ALDEHYDES, AMINES, BORON ACIDS, PHOSPHORUS ACIDS, OXYGEN, AIRCARBON DIOXIDE, AND MIXTURES THEREOF. THE METAL-CONTAINING COMPOSITIONS ARE READILY AND STABLY DISPERSED IN NONPOLAR ORGANIC LIQUIDS. THEY ARE USEFUL AS ADDITIVES IN PLASTICS, RUBBERS, PAINTS, CAULKS, ETC., WHERE THEY FUNCTION AS FILLERS AND THIXOTROPIC AGENTS.

United States Patent 3,766,066 GRQUPS I AND H METAL-CONTAINING MICELLARCOMPLEXES Richard Leo McMillen, Painesville, Ohio, assignor to TheLubrizol Corporation, Wicklilfe, Ohio No Drawing. Continuation-impart ofapplication Ser. No.

5 ,427, Jan. 23, 1970, now abandoned, which is a contmuatron-in-part ofapplication Ser. No. 631,195, Apr. 17, 1967, now Patent No. 3,492,231,which is a continuation-m-part of application Ser. No. 612,332, Jan. 30,1967, now Patent No. 3,384,586, which is a continuatron-in-part ofapplication Ser. No. 535,742, Mar. 21, 1966, now abandoned, which is acontinuation-in-part of application Ser. No. 185,521, Apr. 6, 1962, nowPatent No. 3,242,079. Said application Ser. No. 631,195 being acontinuation-in-part of application Ser. No. 580,575, Sept. 20, 1966,now Patent No. 3,376,222, which is a continuation-in-part ofapplications Ser. No. 323,135, Nov. 12, 1963, now abandoned, and Ser.No. 558,287, June 17, 1966, now Patent No. 3,350,308, both beingcontinuations-in-part of application Ser. No. 309,293, Sept. 16, 1963,now abandoned. Said applicatron Ser. No. 612,332 being acontinuation-in-part of applications Ser. No. 369,271, May 21, 1964, andSer. No. 535,048, Mar. 17, 1966, both now abandoned. Finally, saidapplication Ser. No. 631,195 is also a continuation-in-part ofapplication Ser. No. 535,693, Mar. 21, 1966, now Patent No. 3,372,115,which in turn is a continuation-in-part of said application Ser. No.185,521. This application Oct. 12, 1971, Ser. No.

Int. Cl. C-Om 5/16, 5/22, 7/36 U.S. Cl. 25232.7 E 11 Claims ABSTRACT OFTHE DISCLOSURE Solid, Groups I and II metal-containing micellarcomplexes are prepared by isolating the solid, metal-containmg matterfrom homogenized, overbased organic acids with the aid of suchconversion agents as aliphatic carboxylic acids, water, alcohols,phenols, ketones, aldehydes, amines, boron acids, phosphorus acids,oxygen, air, carbon dioxide, and mixtures thereof. The metal-containingcompositions are readily and stably dispersed in nonpolar organicliquids. They are useful as additives in plastics, rubbers, paints,caulks, etc., where they function as fillers and thixotropic agents.

REFERENCES TO RELATED APPLICATIONS This application is acontinuation-in-part application of my earlier filed copendingapplication Ser. No. 5,427, filed Jan. 23, 1970, now abandoned; which inturn is a contmuatlon-in-part of my earlier application Ser. No. 631,-195, filed Apr. 17, 1967, now U.S. Pat. 3,492,231 (issued Jan. 7, 1970);which in turn is a continuation-in-part of my earlier application Ser.No. 612,332, filed Jan. 30, 1967, now U.S. Pat. 3,384,586 (issued May21, 1968); which 1n 1ts turn is a continuation-in-part of my earlierapplication Ser. No. 535,742, filed Mar. 21, 1966, now abandoned; whichin its turn is a continuation-in-part of my earlier filed applicationSer. No. 185,521, filed Apr. 6, 1962, now U.S. Pat. 3,242,079 (issuedMar. 22, 1966). The aforementioned U.S. Pat. 3,492,231 is also acontinuationm-part of my earlier filed application Ser. No. 580,575,filed Sept. 20, 1966, now U.S. Pat. 3,376,222 (issued Apr. 2, 1968);when in turn is a continuation-in-part of my earlier filed applicationSer. No. 323,135, filed Nov. 12, 1963, now abandoned; and Ser. No.558,287, filed June 17,1966, now U.S. Pat. 3,350,308 (issued Oct. 31,1967); which in their turn are continuations-in-part of my earlier filedapplication Ser. No. 309,293, filed Sept. 16, 1963, now abandoned. Theaforementioned U.S. Pat. 3,384,586 is also a continuation-in-part of myearlier application ice Ser. No. 369,271, filed May 21, 1964, nowabandoned; and Ser. No. 535,048, filed Mar. 17, 1966, now abandoned.Finally, the aforementioned U.S. Pat. 3,492,231 is also acontinuation-in-part of my earlier filed Ser. No. 535,693, filed Mar.21, 1966, now U.S. Pat. 3,372,115 (issued Mar. 5, 1968); which in turnis a continuation-inpart of my earlier noted U.S. Pat. 3,242,079.

This invention relates to solid, metal-containing compositionscharacterized by the ability to be readily and stably dispersed innonpolar organic liquids and to processes for preparing thesecompositions. In particular, the invention concerns isolating solid,metal-containing compositions from non-Newtonian colloidal dispersesystems. In another aspect, the invention relates to processes fortreating non-Newtonian colloidal disperse systems so as to isolate thedesired solid, metal-containing compositions.

In my U.S. Pats. 3,384,586 and 3,492,231, I describe in detail thepreparation of non-Newtonian colloidal disperse systems. Thesenon-Newtonian colloidal disperse systems comprise solid,metal-containing colloidal particles predispersed in a liquid dispersingmedium and as an essential third component, at least one organiccompound which is soluble in said dispersing medium, the molecules ofsaid organic compound being characterized by a hydrophobic portion andat least one polar substituent.

In accordance with the invention claimed in this application, thesenon-Newtonian colloidal disperse systems are further treated so as toisolate a solid, metal-containing composition therefrom. This solid,metal-containing composition is readily and stably dispersed in polarorganic liquids. Furthermore, they can be reduced to powders and addeddirectly to resins, caulks, and the like where they function effectivelyas fillers and thixotropic agents.

The solid, metal-containing compositions of this invention contain theadvantageous properties associated with the non-Newtonian colloidaldisperse systems claimed in the above patents while eliminating otherproblems. For example, it has been found that the presence of theorganic liquid dispersing medium in the non-Newtonian colloidal dispersesystem sometimes interferes with particular uses of the disperse systemsas thixotropes and fillers. For example, mineral oil, which is a commondispersing medium for the disperse systems, sometimes migrates to theinterface or surface of a resinous composition containing the colloidaldisperse system. This interferes with the adherence of coatings andadhesives on the surface or interface. Likewise, economic advantages areassociated with the use of the solid, metal, containing compositions.For example, the cost of shipping and storing is reduced. This is trueeven in those applications Where the organic liquid dispersing medium isdesirable since, the solid, metal-containing compositions, upon reachingtheir destination or at the time when they are to be used can easily bereincorporated into a nonpolar organic liquid dispersing medium toregenerate the non-Newtonian colloidal disperse system. The ease withwhich these solid, metal-containing compositions are readily and stablydispersed within the nonpolar organic liquid diluents makes thisregeneration of the non-Newtonian colloidal disperse systems possible.Obviously, the solid, metal-containing compositions of this inventioncan be employed in the same manner as the non-Newtonian colloidaldisperse systems of the above patents.

In accordance with the foregoing, it is a principal object of theinvention to provide solid, metal-containing compositions. Anotherobject is to provide solid, metal-containing compositions characterizedby being readily and stably dispersed in nonpolar organic liquids. Afurther object is to provide the process for preparing solid, metal- 3 Icontaining compositions from non-Newtonian colloidal disperse systems.

These and other objects of this invention are achieved by providing aprocess for preparing solid, metal-containing compositions comprisingseparating substantially all of the liquid dispersing medium from anon-Newtonian colloidal disperse system which consists essentially ofsolid, metal-containing colloidal particles predispersed in a liquiddispersing medium, and as an essential third component, at least oneorganic compound which is soluble in said disperse medium, the moleculesof said organic compound being characterized by a hydrophobic portionand at least one polar substituent, thereby isolating the desired solid,metal-containing compositions. Stated differently, the process,including the formation of the non- Newtonian colloidal dispersedsystem, comprises homogenizing at least one overbased organic materialhaving a metal ratio of at least three which is homogeneously dispersedin a substantially inert, nonpolar, organic liquid diluent in thepresence of at least one conversion agent, and thereafter separatingfrom the resulting homogenized products substantially all of thenon-polar organic liquid diluent, conversion agent, and water from theremainder of the reaction mixture thereby isolating the desired solid,metal-containing composition.

THE COLLOIDAL DISPERSE SYSTEMS USED AS INTERMEDIATES The terminologydisperse system as used in the specification and claims is a term of artgeneric to colloids or colloidal solutions, e.g., any homogeneous mediumcontaining dispersed entities of any size and state, Jirgensons andStraumanls, A Short Text Book on Colloidal Chemistry, second edition,The MacMillan Co., New York, 1962, page 1. However, the particulardispersed systems of the present invention form a subgenus within thisbroad class of disperse systems, this subgenus being characterized byseveral important features.

This subgenus comprises those dispersed'systems wherein at least aportion of the particles dispersed therein are solid, metal-containingparticles formed in situ. At least about to about 50% are particles ofthis type and preferably, substantially all of said solid particles areformed in situ.

So long as the solid particles remain dispersed in the dispersing mediumas colloidal particles the particle size is not critical. Ordinarily,the particles will not exceed 5000 A. However, it is preferred that themaximum unit particle size be less than about 1000 A. In a particularlypreferred aspect of the invention, the unit particle size is less thanabout 400 A. Systems having a unit particle size in that range of 30 A.to 200 A. give excellent results. The minimum unit particle size is atleast A. and preferably at least about 30 A.

The language unit particle size is intended to designate the averageparticle size of the solid, metal-containing particles assuming maximumdispersion of the individual particles throughout the disperse medium.That is, the unit particle is that particle which corresponds in size tothe average size of the metal-containing particles and is capable ofindependent existence within the disperse system as a discrete colloidalparticle. These metal-containing particles are found in two forms in thedisperse systems. Individual unit particles can be dispersed as suchthroughout the medium or unit particles can form an agglomerate, incombination with other materials (e.g., another metalcontainingparticle, the disperse medium, etc.) which are present in the dispersesystems. These agglomerates are dispersed through the system asmetal-containing particles. Obviously, the particle size of theagglomerate is substantially greater than the unit particle size.Furthermore, it is equally apparent that this agglomerate size issubject to wide variations, even within the same disperse system. Theagglomerate size varies, for example, with the degree of shearing actionemployed in dispersing the unit particles. That is, mechanical agitationof the disperse system tends to break down the agglomerates into theindividual components thereof and disperse these individual componentsthroughout the disperse medium. The ultimate in dispersion is achievedwhen each solid, metal-containing particle is individually dispersed inthe medium. Accordingly, the disperse systems are characterized withreference to the unit particle size, it being apparent to those skilledin the art that the unit particle size represents the average size ofsolid, metal-containing particles present in the system which can existindependently. The average particle size of the metal-containing solidparticles in the system can be made to approach the unit particle sizevalue by the application of a shearing action to the existent system orduring the formation of the disperse system as the particles are beingformed in situ. It is not necessary that maximum particle dispersionexist to have useful disperse systems. The agitation associated withhomogenization of the overbased material and conversion agent producessufficient particle dispersion.

Basically, the solid metal-containing particles are in the form of metalsalts of inorganic acids and low molecular weight organic acids,hydrates thereof, or mixtures of these. These salts are usually thealkali and alkaline earth metal formates, acetates, carbonates, hydrogencarbonates, hydrogen sulfides, sulfites, hydrogen sulfites, and halides,particularly chlorides. In other words, the metalcontaining particlesare ordinarily particles of metal salts, the unit particle is theindividual salt particle and the unit particle size is the averageparticle size of the salt particles which is readily ascertained, as forexample, by conventional X-ray diffraction techniques. Colloidaldisperse systems possessing particles of this type are sometimesreferred to as macromolecular colloidal systems.

Because of the composition of the colloidal disperse systems of thisinvention, the metal-containing particles also exist as components inmicellar colloidal particles. In addition to the solid metal-containingparticles and the disperse medium, the colloidal disperse systems of theinvention are characterized by a third essential component, one which issoluble in the medium and contains in the molecules thereof ahydrophobic portion and at least one polar substituent. This thirdcomponent can orient itself along the external surfaces of the abovemetal salts, the polar groups lying along the surface of these saltswith the hydrophobic portions extending from the salts into the dispersemedium forming micellar colloidal particles. These micellar colloidsinvolve Weak intermolecular forces, e.g., Van der Waals forces, ionicbonds, etc. Micellar colloids represent a type of agglomerate particleas discussed thereinabove. Because of the molecular orientation in thesemicellar colloidal particles, such particles are characterized by ametal containing layer (i.e., the solid metal-containing particles andany metal present in the polar substituent of the third component, suchas the metal in a sulfonic or carboxylic acid salt group), a hydrophobiclayer formed by the hydrophobic portions of the molecules of the thirdcomponent and a polar layer bridging said metal-containing layer andsaid hydrophobic layer, said polar bridging layer comprising the polarsubstituents of the third component of the system, e.g., the

group if the third component is an alkaline earth metal petrosulfonate.

The second essential component of the colloidal disperse system is thedispersing medium. The identity of the medium is not a particularlycritical aspect of the invention as the medium primarily serves as theliquid vehicle in which solid particles are dispersed. The dispersemedium will normally consist of inert organic liquids, that is, liquidswhich are chemically substantially inactive in the particularenvironment in question (the resinous composition). While many of theseinert organic liquids are nonpolar, this is not essential. For example,many of the plasticizers for the resinous components of the compositionare esters, etc. These polar materials can also be used as thedispersing medium or components thereof. The medium can have componentscharacterized by relatively low boiling points, e.g., in the range of 25to 120 C. to facilitate subsequent removal of a portion or substantiallyall of the medium from the polymeric resin composition or the componentscan have a higher boiling point to protect against removal from theresinous composition upon standing or heating. Obviously, there is nocriticality in an upper boiling point limitation on these liquids.

Representative liquids include the alkanes and haloalkanes of five toeighteen carbons, polyhaloand perhaloalkanes of up to about six carbons,the cycloalkanes of five or more carbons, the corresponding alkyland/ orhalo-substituted cycloalkanes, the aryl hydrocarbons, the alkylarylhydrocarbons, the haloaryl hydrocarbons, ethers such as dialkyl ethers,alkylaryl ethers, cycloalkyl ethers, cycloalkylalkyl ethers, al'kylethers of alkylene and polyalkylene 'glycols, dimethyl formamide,dimethyl acetamide, dibasic alkanoic acid diesters, silicate esters, andmixtures of these. Specific examples include petroleum ether, StoddardSolvent, pentane, hexane, octane, isooctane, undecane, tetradecane,cyclopentane, cyclohexane, isopropylcyclohexane, 1,4dimethylcyclohexane, cyclooctane, benzene, toluene, xylene, ethylbenzene, tert-butyl-benzene, halobenzenes especially monoandpolychlorobenzenes such as chlorobenzene per se and 3,4-dichlorotoluene,mineral oils, n-propylether, isopropylether, isobutylether, n-amylether,methyl-n-amylether, cyclohexylether, ethoxycyclohexane, methoxybenzene,isopropoxybenzene, p-methoxytoluene, 1,Z-difluoro-tetrachloroethane,dichlorofluoromethane, 1,2-dibromotetrafiuorethane,trichlorofluoromethane, 1 chloropentane, 1,3 dichlorohexane, formamide,acetamide, dimethylacetamide, diethylacetamide, propionamide,di-isooctyl azelate, heXa-Z-ethylbutoxy disiloxane, etc.

Also useful as dispersing mediums are the low molecular weight, liquidpolymers, generally classified as oligomers, which include the dimers,tetramers, pentamers, etc. Illustrative of this large class of materialsare such liquids as the propylene tetramers, isobutylene dimers, and thelike.

From the standpoint of availability, cost, and performance, the alkyl,cycloalkyl, and aryl hydrocarbons represent a preferred class ofdisperse mediums. Liquid petroleum fractions represent another preferredclass of disperse mediums. Included within these preferred classes are.benzenes and alkylated benzenes, cycloalkanes and alkylatedcycloalkanes, cycloalkenes and alkylated cycloalkenes such as found innaphthene based petroleum fractions, and the alkanes such as found inthe parafiin-based petroleum fractions. Petroleum ether, naphthas,mineral oils, Stoddard Solvent, toluene, xylene, etc., and mixturesthereof are examples of economical sources of suitable inert organicliquids which can function as the disperse medium in the colloidaldisperse systems of the present invention.

The most preferred disperse systems are those containing at least somemineral oil as a component of the disperse medium. These systems areparticularly effective as lubricants for the polymeric composition, animportant feature in extrusion processes. Any amount of mineral oil isbeneficial in this respect. However, in this preferred class of systems,it is desirable that mineral oil comprise at least about 1% by weight ofthe total medium, and preferably at least about 5% by weight. Thosemediums comprising at least by weight mineral oil are especially useful.As will be seen hereinafter, mineral oil can serve as the exclusivedisperse medium.

In addition to the solid, metal-containing particles in the dispersemedium, the two essential elements of any disperse system, the dispersesystems employed in the polymeric compositions of the invention requirea third essential component. This third component is an organic compoundwhich is soluble in the disperse medium, and the molecules of which arecharacterized by a hydrophobic portion and at least one polarsubstituent. As explained, infra, the organic compounds suitable as athird component are extremely diverse. These compounds are inherentconstituents of the disperse systems as a result of the methods used inpreparing the systems. Further characteristics of the components areapparent from the following discussion of methods for preparing thecolloidal disperse systems.

PREPARATION OF THE DISPERSE SYSTEMS Broadly speaking, the colloidaldisperse systems of the invention are prepared by treating a singlephase homogeneous, Newtonian system of an overbased, superbased, orhyperbased, organic compound with a conversion agent, usually an activehydrogen containing compound, the treating operation being simply athorough mixing together of the two components, i.e., homogenization.This treatment converts these single phase systems into thenon-Newtonian colloidal disperse systems utilized in conjunction withthe polymeric resins of the present invention.

The terms overbased, superbased, and hyperbased, are terms of art whichare generic to well known classes of metal-containing materials whichhave generally been employed as detergents and/ or dispersants inlubricating oil compositions. These overbased materials have also beenreferred to as complexes, metal complexes, high-metal containing salts,and the like. Overbased materials are characterized by a metal contentin excess of that which would be present according to the stoichiometryof the metal and the particular organic compound reacted with the metal,e.g., a carboxylic or sulfonic acid. Thus, if a monosulfonic acid,

is neutralized with a basic metal compound, e.g., calcium hydroxide, thenormal metal salt produced will contain one equivalent of calcium foreach equivalent of acid, i.e.,

However, as is well known in the art, various processes are availablewhich result in an inert organic liquid solution of a product containingmore than the stoichiometric amount of metal. The solutions of theseproducts are referred to herein as overbased materials. Following theseprocedures, the sulfonic acid or an alkali or alkaline earth metal saltthereof can be reacted with a metal base and the product will contain anamount of metal in excess of that necessary to neutralize the acid, forexample, 4.5 times as much metal as present in the normal salt or ametal excess of 3.5 equivalents. The actual stoichiometric excess ofmetal can vary considerably, for example, from about 0.1 equivalent toabout 30 or more equivalents depending on the reactions, the processconditions, and the like. These overbased materials useful in preparingthe disperse systems will contain from about 3.5 to about 30 or moreequivalents of metal for each equivalent of material which is overbased.

In the present specification and claims the term overbased is used todesignate materials containing a stoichiometric excess of metal and is,therefore, inclusive of those materials which have been referred to inthe art as overbased, superbased, hyperbased, etc., as discusse supra.

The terminology metal ratio is used in the prior art and herein todesignate the ratio of the total chemical equivalents of the metal inthe overbased material (e.g., a metal sulfonate or carboxylate) to thechemical equivalents of the metal in the product which would be expectedto result in the reaction between the organic material to be overbased(e.g., sulfonic or carboxylic acid) and the metal-containing reactant(e.g., calcium hydroxide, barium oxide, etc.) according to the knownchemical reactivity and stoichiometry of the two reactants. Thus, in thenormal calcium sulfonate discussed above, the metal ratio is one and inthe overbased sulfonate, the metal ratio is 4.5. Obviously, if there ispresent in the material to be overbased more than one compound capableof reacting with the metal, the metal ratio of the product will dependupon whether the number of equivalents of metal in the overbased productis compared to the number of equivalents expected to be present for agiven single component or a combination of all such components.

Generally, these overbased materials are prepared by treating a reactionmixture comprising the organic material to be overbased, a reactionmedium consisting essentially of at least one inert, organic solvent forsaid organic material, a stoichiometric excess of a metal base, and apromoter with an acidic material. The methods for preparing theoverbased materials as well as an extremely diverse group of overbasedmaterials are well known in the prior art and are disclosed, for examplein the following US. patents: 2,616,904; 2,616,905; 2,616,906;2,616,911; 2,616,924; 2,616,925; 2,617,049; 2,695,910; 2,723,234;2,723,235; 2,723,236; 2,760,970; 2,767,164; 2,767,209; 2,777,874;2,798,852; 2,839,470; 2,856,359; 2,859,360; 2,856,361; 2,861,951;2,883,340; 2,915,517; 2,959,551; 2,968,642; 2,971,014; 2,989,463;3,001,981; 3,027,325; 3,070,581; 3,108,960; 3,147,232; 3,133,019;3,146,201; 3,152,991; 3,155,616; 3,170,880; 3,170,881; 3,172,855;3,194,823; 3,223,630; 3,232,883; 3,242,079; 3,242,080; 3,250,710;3,256,186; 3,274,135. The disclosures of these patents discloseexemplary processes for synthesizing the overbased materials used inproducing the disperse systems of the invention and are, accordingly,incorporated herein by reference for their disclosures of theseprocesses, materials which can be overbased, suitable metal bases,promoters, and acidic materials, as well as a variety of specificoverbased products.

An important characteristic of the organic materials which are overbasedis their solubility in the particular reaction medium utilized in theoverbasing process. As the reaction medium used previously has normallycomprised petroleum fractions, particularly mineral oils, these organicmaterials have generally been oil-soluble. However, if another reactionmedium is employed (e.g. aromatic hydrocarbons, aliphatic hydrocarbons,kerosene, etc.) it is not essential that the organic material be solublein mineral oil as long as it is soluble in the given reaction medium.Obviously, many organic materials which are soluble in mineral oils willbe soluble in many of the other indicated suitable reaction mediums. Itshould be apparent that the reaction medium usually becomes the dispersemedium of the colloidal disperse system or at least a component thereofdepending on whether or not additional inert organic liquid is added aspart of the reaction medium or the disperse medium.

Materials which can be overbased are generally oil-soluble organic acidsincluding phosphorus acids, thiophosphorus acids, sulfur acids,carboxylic acids, thiocarboxylic acids, and the like, as well as thecorresponding alkali and alkaline earth metal salts thereof.Representative examples of each of these classes of organic acids aswell as other organic acids, e.g., nitrogen acids, arsenic acids,

etc. are disclosed-along with methods of preparing overbased productstherefrom in the above cited patent and are, accordingly, incorporatedherein by reference. Pat. 2,777,874 identified organic acids suitablefor preparing overbased materials which can beconverted to dispersesystems for, use in the resinous compositions of the invention.Similarly, 2,616,904; 2,695,910; 2,767,164; 2,767,209; 3,147,232;3,274,135; etc. disclose a variety of organic acids suitable forpreparing overbased materials as well as representative examples ofoverbased products prepared from such acids. Overbased acids wherein theacid is a phosphorus acid, a thiophosphorus acid, phosphorus acid-sulfuracid combination, and sulfur acid prepared from polyolefins aredisclosed in 2,883,340; 2,915,- 517; 3,001,981; 3,108,960; and3,232,883. Overbased phenates are disclosed in 2,959,551 while overbasedketones are found in 2,798,852. A variety of overbased materials derivedfrom oil-soluble metal-free, non-tautomeric neutral and basic organicpolar compounds such as esters, amines, amides, alcohols, ethers,sulfides, sulfoxides, and the like are disclosed in 2,968,642;2,971,014; and 2,989,- 463. Another class of materials which can beoverbased are the oil-soluble, nitro-substituted alphatic hydrocarbons,particularly nitro-substituted polyolefins such as polyethylene,polypropylene, polyisobutylene, etc. Materials of this type areillustrated in 2,959,551. Likewise, the oil-soluble reaction product ofalkylene polyamines such as propylene diamine or N-alkylatedpropylenediamine with formaldehyde or formaldehyde producing compound(e.g., paraformaldehyde) can be overbased. Other compounds suitable foroverbasing are disclosed in the above-cited patents or are otherwisewell-known in the art.

The organic liquids used as the disperse mediumin the colloidal dispersesystem can be used as solvents for the overbasing process.

The metal compounds used in preparing the overbased materials arenormally the basic salts of metals in Group I-A and Group II-A of thePeriodic Table although other metals such as lead, zinc, manganese, etc.can be used in the preparation of overbased materials. The anionicportion of the salt can be hydroxyl, oxide, carbonate, hydrogencarbonate, nitrate, sulfite, hydrogen sulfite, halide, amide, sulfateetc. as disclosed in the above-cited patents. For purposes of thisinvention the preferred overbased materials are prepared from thealkaline earth metal oxides, hydroxides, and alcoholates such as thealkaline earth metal lower alkoxides. The most preferred dispersesystems of the invention are made from overbased materials containingcalcium and/ or barium as the metal.

The promoters, that is, the materials which permit the incorporation ofthe excess metal into the overbased material, are also quite diverse andwell known in the art as evidenced by the cited patents. A particularlycomprehensive discussion of suitable promoters is found in 2,777,874;2,695,910; and 2,616,904. These include the alcoholic and phenolicpromoters which are preferred. The alcoholic promoters include thealkanols of one to about twelve carbon atoms such as methanol, ethanol,amyl alcohol, octanol, isopropanol, and mixtures of these and the like.Phenolic promoters include a variety of hydroxysubstituted benzenes andnaphthalenes. A particularly useful class of phenols are the alkylatedphenols of the type listed in 2,777,874, e.g., heptylphenols,octylphenols, and nonylphenols. Mixtures of various promoters aresometimes used.

Suitable acidic materials are also disclosed in the above cited patents,for example, 2,616,904. Included within the known group of useful acidicmaterials are liquid acids such as formic acid, acetic acid, nitricacid, sulfuric acid, hydrochloric acid, hydrobromic acid, carbamic acid,substituted carbamic acids, etc. Acetic acid is a very useful acidicmaterial although inorganic acidic materials such as HCl, S0 S0 CO H S,N 0 etc., are ordinarily employed as the acidic materials. The mostpreferred acidic materials are carbon dioxide and acetic acid.

In preparing overbased materials, the material to be overbased, aninert, non-polar, organic solvent therefor, the metal base, thepromoter, and the acidic material are brought together and a chemicalreaction ensues. The exact nature of the resulting overbased product isnot known. However, it can be adequately described for purposes of thepresent specification as a single phase homogeneous mixture of thesolvent and (1) either a metal complex formed from the metal base, theacidic material, and the material being overbased and/or (2) anamorphous metal salt formed from the reaction of the acidic materialwith the metal base and the material which is said to be overbased.Thus, if mineral oil is used as the reaction medium, petrosulfonic acidas the material which is overbased, Ca(OH) as the metal base, and carbondioxide as the acidic material, the resulting overbased material can bedescribed for purposes of this invention as an oil solution of either ametal containing complex of the acidic material, the metal base, and thepetrosulfonic acid or as an oil solution of amorphous calcium carbonateand calcium petrosulfonate. Since the overbased materials are well-knownand as they are used merely as intermediates in the preparation of thedisperse systems employed herein, the exact nature of the materials isnot critical to the present invention.

The temperature at which the acidic material is contacted with theremainder of the reaction mass depends to a large measure upon thepromoting agent used. With a phenolic promoter, the temperature usuallyranges from about 80 C. to 300 C., and preferably from about 100 C. toabout 200 C. When an alcohol or mercaptan is used as the promotingagent, the temperature usually will not exceed the reflux temperature ofthe reaction mixture and preferably will not exceed about 100 C.

In view of the foregoing, it should be apparent that the overbasedmaterials may retain all or a portion of the promoter. That is, if thepromoter is not volatile (e.g., an alkyl phenol) or otherwise readilyremovable from the overbased material, at least some promoter remains inthe overbased product. Accordingly, the disperse systems made from suchproducts may also contain the promoter. The presence or absence of thepromoter in the overbased material used to prepare the disperse systemand likewise, the presence or absence of the promoter in the colloidaldisperse systems themselves does not represent a critical aspect of theinvention. Obviously, it is within the skill of the art to select avolatile promoter such as a lower alkanol, e.g., methanol, ethanol,etc., so that the promoter can be readily removed prior to forming thedisperse system or thereafter.

A preferred class of overbased materials used as starting materials inthe preparation of the disperse systems of the present invention are thealkaline earth metal-overbased oil-soluble organic acids, preferablythose containing at least twelve aliphatic carbons although the acidsmay contain as few as eight aliphatic carbon atoms if the acid moleculeincludes an aromatic ring such as phenyl, naphthyl, etc. An especiallypreferred class are the calcium overbased organic acids. This especiallypreferred class of overbased materials, processes for homogenizing them,and processes for isolating the desired, solid calcium-containingcomposition in the form of a micellar complex art illustrated, discussedand claimed in my copending applications Ser. No. 886,790 filed Dec. 19,1969, and Ser. No. 179,160 filed on or about Sept. 9, 1971, bothentitled Calcium-Containing Micellar Complexes which are expresslyincorporated herein by reference for their full description of how tomake and use this especially preferred aspect of the invention.Representative organic acids suitable for preparing these overbasedmaterials are discussed and identified in detail in the abovecitedpatents. Particularly 2,616,904 and 2,777,874 disclose a variety of verysuitable organic acids. For reasons of economy and performance,overbased oil-soluble carboxylic and sulfonic acids are particularlysuitable. Illustrative of the carboxylic acids are palmitic acid,stearic acid, myristic acid, oleic acid, linoleic acid, behenic acid,hexatriacontanoic acid, tetrapropylene-substituted glutaric acid,polyisobutene (M.W.-5000)-substituted succinic acid, polypropylene(M.W.-10,000)-substituted succinic acid, octadecyl-substituted adipicacid, chlorostearic acid, 9-methylstearic acid, dichlorostearic acid,stearyl'benzoic acid, eicosane-substituted naphthoic acid,dilauryl-decahydronaphthalene carboxylic acid, didodecyl-Tetralincarboxylic acid, dioctylcyclohexane carboxylic acid, mixtures of theseacids, their alkali and alkaline earth metal salts, and/or theiranhydrides. Of the oil-soluble sulfonic acids, the mono-, di-, andtri-aliphatic hydrocarbon substituted aryl sulfonic acids and thepetroleum sulfonic acids (petrosulfonic acids) are particularlypreferred. Illustrative examples of suitable sulfonic acids includemahogany sulfonic acids, petrolatum sulfonic acids,monoeicosanesubstituted naphthalene sulfonic acids, dodecylbenzenesulfonic acids, didodecylbenzene sulfonic acids, dinonylbenzene sulfonicacids, cetyl-chlorobenzene sulfonic acids, dilauryl beta-naphthalenesulfonic acids, the sulfonic acid derived by the treatment ofpolyisobutene having a molecular weight of 1,500 with chlorosulfonicacid, nitronaphthalenesulfonic acid, parafiin wax sulfonic acid,cetylcyclopentane sulfonic acid, lauryl-cyclohexanesulfonic acids,polyethylene (M.W.--750) sulfonic acids, etc. Obyiously, it is necessarythat the size and number of aliphatic groups on the aryl sulfonic acidsbe sufiicient to render the acids soluble. Normally the aliphatic groupswill be alkyl and/or alkenyl groups such that the total number ofaliphatic carbons is at least twelve.

Within this preferred group of overbased carboxylic and sulfonic acids,the barium and calcium overbased mono-, di-, and tri-alkylated benzeneand naphthalene (including hydrogenated forms thereof), petrosulfonicacids, and higher fatty acids are especially preferred. Illustrative ofthe synthetically produced alkylated benzene and naphthalene sulfonicacids are those containing alkyl substituents having from 8 to about 30carbon atoms therein. Such acids include di-isododecyl-benzene sulfonicacid, wax-substituted phenol sulfonic acid, wax-substituted benzenesulfonic acids, polybutene-substituted sulfonic acid,cetyl-chlorobenzene sulfonic acid, di-cetylnaphthalene sulfonic acid,di-lauryldiphenylether sulfonic acid, diisononylbenzene sulfonic acid,di-isooctadecylbenzenesulfonic acid, stearylnaphthalene sulfonic acid,and the like. The petroleum sulfonic acids are a well known artrecogniz/ed class of materials which have been used as startingmaterials in preparing overbased products since the inception ofoverbasing techniques as illustrated by the above patents. Petroleumsulfonic acids are obtained by treating refined or semi-refinedpetroleum oils with concentrated or fuming sulfuric acid. These acidsremain in the oil after the settling out of sludges. These petroleumsulfonic acids, depending on the nature of the petroleum oils from whichthey are prepared, are oil-soluble alkane sulfonic acids,alkyl-substituted cycloaliphatic sulfonic acids including cycloalkylsulfonic acids and cycloalkene sulfonic acids, and alkyl, alkaryl, oraralkyl substituted hydrocarbon aromatic sulfonic acids including singleand condensed aromatic nuclei as well as partially hydrogenated formsthereof. Examples of such petrosulfonic acids include mahogany sulfonicacid, white oil sulfonic acid, petrolatum sulfonic acid, petroleumnaphthene sulfonic acid, etc. This especially preferred group ofaliphatic fatty acids includes the saturated and unsaturated higherfatty acids containing from 12 to about 30 carbon atoms. Illustrative ofthese acids are lauric acid, palmitic acid, oleic acid, linoleic acid,linolenic acid, oleo-stearic acid, stearic acid, myristic acid, andundecalinic acid, alpha-chlorostearic acid, and alpha-nitrolauric acid.

As shown by the representative examples of the pre ferred classes ofsulfonic and carboxylic acids, the acids may contain non-hydrocarbonsubstituents such as halo, nitro, alkoxy, hydroxyl, and the like.

It is desirable that the overbased materials used toprepare the dispersesystem have a metal ratio of at least about 3.0 and preferably about4.5. An especially suitable group of the preferred sulfonic acidoverbased materials has a metal ratio of at'least about 7.0. Whileoverbased materials having a metal ratio of 75 have been prepared,normally the maximum metal ratio will not exceed about 30 and, in mostcases, not more than about 20.

The overbased materials used in preparing the colloidal disperse systemsutilized in the polymeric composition of the invention contain fromabout 15% to about 70% by weight of metal-containing components. Asexplained hereafter, the exact nature of these metal containingcomponents is not known. It is theorized that the metal base, the acidicmaterial, and the organic material being overbased form a metal complex,this complex being the metal-containing component of the overbasedmaterial. On the other hand, it has also been postulated that the metalbase and the acidic material form amorphous metal compounds which aredissolved in the inert organic reaction medium and the material which issaid to be overbased. The material which is overbased may itself be ametal-containing compound, e.g., a carboxylic or sulfonic acid metalsalt. In such a case, the metal-containing components of hte overbasedmaterial would be both the amorphous compounds and the acid salt. Theexact nature of these overbased materials is obviously not critical inthe present invention since these materials are used only asintermediates. The remainder of the overbased materials consistessentially of the inert organic reaction medium and any promoter whichis not removed from the overbased product. For purposes of thisapplication, the organic material which is subjected to overbasing isconsidered a part of the metal containing components. Normally, theliquid reaction medium constitutes at least about 30% by weight of thereaction mixture utilized to prepare the overbased materials. Asmentioned above, the colloidal disperse systems used 1n the compositionof the present invention are prepared by homogenizing a conversionagent" and the overbased starting material. Homogenization is achievedby vigorous agitation of the two components, preferably at the refluxtemperature or a temperature slightly below the reflux temperature. Thereflux temperaure normally will depend upon the boiling point of theconversion agent. However, homogenization may be achieved within therange of about 25 C. to about 200 C. or slightly higher. Usually, thereis no real advantage in exceeding 150 C.

The concentration of the conversion agent necessary to achieveconversion of the overbased material is usually within the range of fromabout 1% to about 80% based upon the weight of the overbased materialexcluding the weight of the inert, organic solvent and any promoterpresent therein. Preferably at least about and usually less than about60% by weight of the conversion agent is employed. Concentrations beyond60% appear to afford no additional advantages.

The terminology conversion agent as used in the specification and claimsis intended to describe a class of very diverse materials which possessthe property of being able to convert the Newtonian homogeneous,single-phase, overbased materials into non-Newtonian colloidal dispersesystems. The mechanism by which conversion is accomplished is notcompletely understood. However, with the exception of oxygen, carbondioxide, air and mixtures of two or more of these, these conversionagents all possess active hydrogens. The conversion agents include loweraliphatic carboxylic acids, water, aliphatic alcohols, cycloaliphaticalcohols, arylaliphatic alcohols, phenols, ketones, aldehydes, amines,boron acids, phosphorus acids, oxygen, air, and carbon dioxide. Mixturesof two or more of these conversion agents are also useful. Particularlyuseful conversion agents are discussed below.

The lower aliphatic carboxylic acids are those contain ing less thanabout eight carbon atoms in the molecule.

Examples 'ofthis class of acids are formic acid, acetic acid,propionic'acid, butyric acid, valeric acid, isovaleric acid,isobutyric'acid, caprylic acid, heptanoic acid, chloroaceticacid,'dichloroacetic acid, trichloroacetic acid, etc. Formicacid,'acetic acid, and pr'opionic'acid, are preferred with acetic acidbeing especially suitable. It isto be understood that the anhydrides ofthese acids are also useful and, for

the purposes of the specification and claims of this invention, the termacid is intended toinclude both the acid per se and the anhydride of theacid.

Useful alcohols include aliphatic, cycloaliphatic, and arylaliphaticmonoand polyhydroxy alcohols. Alcohols having less than about twelvecarbons are especially useful while the lower alkanols, i.e., alkanolshaving less than about eight carbon atoms are preferred for reasons ofeconomy and effectiveness in the "process. Illustrative are the alkanolssuch as methanol, ethanol, isopropanol, npropanol, isobutanol, tertiarybutanol, isooctanol, dodecanol, n-pentanol, etc.; cycloalkyl alcoholsexemplified by cyclopentanol, cyclohexanol, 4-methylcyclohexanol, 2-cyclohexylethanol, cyclopentylmethanol, etc.; phenyl aliphatic alkanolssuch as benzyl alcohol, 2-phenylethanol, and cinnamyl alcohol; alkyleneglycols of up to about six carbon atoms and mono-lower alkyl ethersthereof such as monomethylether of ethylene glycol, diethylene glycol,ethylene glycol, trimethylene glycol, hexamethylene glycol, tirethyleneglycol, 1,4-butanediol, 1,4-cyclohexanediol, glycerol, andpentaerythritol.

The use of a mixture of water and one or more of the alcohols isespecially effective for converting the overbased materials to colloidaldisperse systems. Such combinations often reduce thev length of timerequired for the process. Any water-alcohol combination is effective buta very effective combination is a mixture of one or more alcohols andwater in a weight ratio of alcohol to water of from about 0.05:1 toabout 24:1. Preferably, at least one lower alkanol ispresent in thealcohol component of these water-alkanol mixtures. Water-alkanolmixtures wherein the alcoholic portion is one or more lower alkanols areespecially suitable. Alcohol:water conversions are illustrated inco-pending application Ser. No. 535,693, filed Mar. 21, 1966, now US.Pat. 3,372,115.

Phenols suitable for use as conversion agents include phenol, naphthol,ortho-cresol, para-cresol, catechol, mixtures of cresol,para-tert-butylphenol, and other 'lower alkyl substituted phenols,meta-polyisobutene(M.W.-- 35 0)-substituted phenol, and the like.

Other useful conversion agents include lower aliphatic aldehydes andketones, particularly lower alkyl aldehydes and lower alkyl ketones suchas acetaldehydes, propionaldehydes, butyraldehydes, acetone, methylethylketone, diethyl ketone. Various aliphatic, cycloaliphatic, aromatic, andheterocyclic amines are also useful providing they contain at least oneamino group having at least one active hydrogen attached thereto.Illustrative of these amines are the monoand di-alkylamines,particularly monoand di-lower alkylamines, such as methylamine,ethylamine, propylamine, dodecylamine, methyl ethylamine, diethylamine;the cycloalkylamines such as cyclohexylamine, cyclopentylamine, and thelower alkyl substituted cycloalkylamines such as3-methylcyclohexylamine; 1,4-cyclohexylenediamine; arylamines suchasaniline, mono-, di-, and tri-, lower alkyl-substituted phenyl amines,naphthylamines, 1,4-phenylene diamines; lower alkanol amines such asethanolamine and diethanolamine; alkylenediamines such as ethylenediamine, triethylene tetramine, propylene diamines, octamethylenediamines and heterocyclic amines such as piperazine,4-aminoethylpiperazine, 2-octadecyl-imidazoline, and oxazolidine. Boronacids are also useful conversion agents and include bornic acids (e.g.,alkyl-B(OH) or aryl-B(OH boric'acid (i.e., H 30 tetraboric acid,metaboric acid, and esters of such boron acids.

The phosphorus acids are useful conversion agents and include thevarious alkyl and aryl phosphinic acids, phosphinus acids, phosphonicacids, and phosphonous acids. Posphorus acids obtained by the reactionof lower alkanols or unsaturated hydrocarbons such as polyisobuteneswith phosphorus oxides and phosphorus sulfides are particularly useful,e.g., P O and P 8 Oxygen, carbon dioxide, air, and various mixtures ofoxygen and carbon dioxide can be used as conversion agents. However, itis preferable to use these conversion agents in combination with one ormore of the foregoing conversion agents. For example, the combination ofwater and carbon dioxide is particularly effective as a conversion agentfor transforming the overbased materials into a colloidal dispersesystem.

As previously mentioned, the overbased materials are single phasehomogeneous systems. However, depending on the reaction conditions andthe choice of reactants in preparing the overbased materials, theresometimes are present in the product insoluble contaminants. Thesecontaminants are normally unreacted basic materials such as calciumoxide, barium oxide, calcium hydroxide, barium hydroxide, or other metalbase materials used as a reactant in preparing the overbased material.It has been found that a more uniform colloidal disperse system resultsif such contaminants are removed prior to homogenizing the overbasedmaterial with the conversion agents. Obviously a more uniform dispersesystem makes it possible to achieve reproducibility of properties inresinous compositions containing such systems. Accordingly, it ispreferred that any insoluble contaminants in the overbased materials beremoved prior to converting the material in the colloidal dispersesystem. The removal of such contaminants is easily accomplished byconventional techniques such as filtration or centrifugation. It shouldbe understood however, that the removal of these contaminants, whiledesirable for reasons just mentioned, is not an absolute essentialaspect of the invention and useful products can be obtained whenoverbased materials containing insoluble contaminants are converted tothe colloidal disperse systems.

The conversion agents or a proportion thereof may be retained in thecolloidal disperse system. The conversion agents are however, notessential components of these disperse systems and it is usuallydesirable that as little of the conversion agents as possible beretained in the disperse systems. Since these conversion agents do notreact with the overbased material in such a manner as to be permanentlybound thereto through some type of chemical bonding, it is normally asimple matter to remove a major proportion of the conversion agents and,generally substantially all of the conversion agents. Some of theconversion agents have physical properties which make them readilyremovable from the disperse systems. Thus, most of the free carbondioxide and/or oxygen gradually escapes from the disperse system duringthe homogenization process or upon standing thereafter. Since the liquidconversion agents are generally more volatile than the remainingcomponents of the disperse system, they are readily removable byconventional devolatilization techniques, e.g., heating, heating atreduced pressures, and the like. For this reason, it may be desirable toselect conversion agents which will have boiling points which are lowerthan the remaining components of the disperse system. This is anotherreason why the lower alkanols, mixtures thereof, and lower alkanolwatermixtures are preferred conversion agents.

Again, it is not essential that all of the conversion agent be removedfrom the disperse systems. In fact, useful disperse systems foremployment in the resinous compositions of the invention result withoutremoval of the conversion agents. However, from the standpoint ofachieving uniform results, it is generally desirable to remove theconversion agents, particularly where they are volatile. In some cases,the liquid conversion agents may facilitate the mixing of the colloidaldisperse system with the polymeric resin material. In such cases, it isadvantageous to permit the conversion agents to remain in the dispersesystem until it is mixed with the polymeric resin. Thereafter, theconversion agents can be removed from the mixture of the disperse systemand polymeric resins by conventional devolatilization techniques ifdesired.

To better illustrate the colloidal disperse systems utilized in theinvention, the procedure for preparing a preferred system is describedbelow:

THE OVERBASED MATERIAL As stated above, the essential materials forpreparing an overbased product are (1) the organic material to beoverbased, (2) an inert, non-polar organic solvent for the organicmaterial, (3) a metal base, (4) a promoter, and (5) an acidic material.In this example, these materials are (1) calcium petrosulfonate, (2)mineral oil, (3) calcium hydroxide, (4) a mixture of methanol,isobutanol, and n-pentanol, and (5) carbon dioxide.

A reaction mixture of 1305 grams of calcium sulfonate having a metalratio of 2.5 dissolved in mineral oil, 220 grams of methyl alcohol, 72grams of isobutanol, and 38 grams of n-pentanol is heated to 35 C. andsubjected to the following operating cycle four times: mixing with 143grams of calcium hydroxide and treating the mixture with carbon dioxideuntil it has a base number of 32-39. The resulting product is thenheated to 155 C. during a period of 9 hours to remove the alcohols andthen filtered at this temperature. The filtrate is a calcium overbasedpetrosulfonate having a metal ratio of 12.2.

CONVERSION TO A COLLOIDAL DISPERSE SYSTEM A mixture of 150 parts of theoverbased material, 15 parts of methyl alcohol, 10.5 parts of n-pentanoland 45 parts of water is heated under reflux conditions at 71- 74 C. for13 hours. The mixture becomes a gel. It is then heated to 144 over aperiod of 6 hours and diluted with 126 parts of mineral oil having aviscosity of 2000 SUS at F. and the resulting mixture heated at 144 C.for an additional 4.5 hours with stirring. This thickened product is acolloidal disperse system of the type contemplated by the presentinvention.

The disperse systems of the invention are characterized by threeessential components: (A) solid, metal-containing particles formed insitu, (B) an inert, non-polar, organic liquid which functions as thedisperse medium, and (C) an organic compound which is soluble in the disperse medium and the molecules of which are characterized by ahydrophobic portion and at least one polar substituent. In the colloidaldisperse system described immediately above, these components are asfollows: (A) calcium carbonate in the form of solid particles, (B)mineral oil, and (C) calcium petrosulfonate.

From the foregoing example, it is apparent that the solvent for thematerial which is overbased becomes the colloidal disperse medium or acomponent thereof. Of course, mixtures of other inert liquids can besubstituted for the mineral oil or used in conjunction with the mineraloil prior to forming the overbased material. Moreover, after theoverbased material is prepared, additional liquid material, e.g., aplasticizer for the resin can be added if desired, to form a part of thedisperse medium. It is also readily seen that the solid,metal-containing particles formed in situ possess the same chemicalcomposition as would the reaction products of the metal base and theacidic material used in preparing the overbased materials. Thus, theactual chemical identity of the metal containing particles formed insitu depends upon both the particular metal base or bases employed andthe particular acidic material or materials reacted therewith. Forexample, if the metal base used in preparing the overbased material werebarium oxide and if the acidic material was a mixture of formic andacetic acids, the metal-containing particles formed in situ would bebarium formates and barium acetates.

However, the physical characteristics of the particles formed in situ inthe conversion step are quite different from the physicalcharacteristics of any particles present in the homogeneous,single-phase overbased material which is subjected to the conversion.Particularly, such physical characteristics as particle size andstructure are quite different. The solid, metal-containing particles ofthe colloidal disperse systems are of a size s-ufficient for detectionby X-ray diffraction. The overbased material prior to conversion are notcharacterized by the presence of these detectable particles.

X-ray diffraction and electron microscope studies have been made of bothoverbased organic materials and colloidal disperse systems preparedtherefrom. These studies establish the presence in the disperse systemsof the solid, metal-containing salts. For example, in the dispersesystem prepared herein above, the calcium carbonate is present as solidcalcium carbonate having a particle size of about 40 to 50 A. (unitparticle size) and interplanar spacing (dA.) of 3.035. But X-raydiffraction studies of the overbased material from which it was preparedindicate the absence of calcium carbonate of this type. In fact, calciumcarbonate present as such, if any, appears to be amorphous and insolution. While applicant does not intend to be bound by any theoryoffered to explain the changes which accompany the conversion step, itappears that conversion permits particle formation and growth. That is,the amorphous, metal-containing apparently dissolved salts or complexespresent in the overbased material form solid, metal-containing particleswhich by a process of particle growth become colloidal particles. Thus,in the above example, the dissolved amorphous calcium carbonate salt orcomplex is transformed into solid particles which then grow. In thisexample, they grow to a size of 40 to 50 A. In many cases, theseparticles apparently are crystallites. Regardless of the correctness ofthe postulated mechanism for in situ particle formation the fact remainsthat no particles of the type predominant in the disperse systems arefound in the overbased materials from which they are prepared.Accordingly, they are unquestionably formed in situ during conversion.

As these solid metal-containing particles formed in situ come intoexistence, they do so as pre-wet, pre-dispersed solid particles whichare inherently uniformly distributed throughout the other components ofthe disperse system. The liquid disperse medium containing these pre-wetdispersed particles is readily incorporated into various polymericcompositions thus facilitating the uniform distribution of the particlesthroughout the polymeric resin composition. This pre-wet, pre-dispersedcharacter of the solid metal-containing particles resulting from theirin situ formation is, thus, an extremely important feature of thedisperse systems.

In the foregoing example, the third component of the disperse system(i.e., the organic compound which is soluble in the disperse medium andwhich is characterized by molecules having a hydrophobic portion and apolar substituent) is calcium petrosulfonate,

wherein R is the residue of the petrosulfonic acid. In this case, thehydrophobic portion of the molecule is the hydrocarbon moiety ofpetrosulfonic, i-.e., R The polar substituent is the metal salt moiety,

The hydrophobic portion of the organic compound is a hydrocarbon radicalor a substantially hydrocarbon radical containing at least about twelvealiphatic carbon a [16 atoms. Usually the hydrocarbon portion is analiphatic or cycloaliphatic hydrocarbon radical although aliphatic orcycloaliphatic substituted aromatic hydrocarbon radicals are alsosuitable. In other words, the hydrophobic portion of the organiccompound is the residue of the organic material which is overbased minusits polar substituents. For example, if the material to be overbased isa carboxylic acid, sulfonic acid, or phosphorus acid, the hydrophobicportion is the residue of these acids which would result from theremoval of the acid functions. Similarly, if the material to beoverbased is a phenol, anitro-substituted polyolefin, or an amine, thehydrophobic portion of the organic compound is the radical resultingfrom the removal of the hydroxyl, nitro, or amino group respectively. Itis the hydrophobic portion of the molecule which renders the'organiccompound soluble in the solvent used in the overbasing process and laterin the disperse medium.

Obviously, the. polar portion of these organic compounds are the polarsubstituents such as the' acid salt moiety discussed above. When thematerial to be overbased contains polar substituents which will reactwith the basic metal compound used in overbasing, for example, acidgroups such as carboxy, sulfino, hydroxysulfonyl, and phosphorus acidgroups or hydroxyl groups, the polar substituent of the third componentis the polar group formed from the reaction. Thus, the polar substituentis the corresponding acid metal salt group or hydroxyl group metalderivative, e.g., an alkali or alkaline earth metal sulfonate,carboxylate, sulfinate, alcoholate, or phenate.

On the other hand, some of the materials to be overbased contained polarsubstituents which ordinarily do not react with metal bases. Thesesubstituents include nitro, amino, ketocarboxyl, carboalkoxy, etc. Inthe disperse systems derived from overbased materials of this type thepolar substituents in the third component' are unchanged from theiridentity in the material which was originally overbased.

The identity of the third essential component of the disperse systemdepends upon the identity of the starting materials (i.e., the materialto be overbased and the metal base compound) used in preparing theoverbased material. Once the identity of these starting materials 28known, the identity of the third component in the colloidal dispersesystem is automatically established. Thus, from the identity of theoriginal material, the identity of the hydrophobic portion of the thirdcomponent in the disperse system is readily established as being theresidue of that material minus the polar substituents attached thereto.The identity of the polar substituents on the third component isestablished as a matter of chemistry. If the polar groups on thematerial to be overbased undergo reaction with the metal base, forexample, if they are acid functions, hydroxy groups, etc., the'polarsubstituent in the final product will correspond to the reaction productof the original substituent and the metal base. On the other hand, ifthe polar substituent in the material to be overbased is one which doesnot react withmetal bases, then the polar substituent of the thirdcomponent is the same as the original substituent.

As previously mentioned, this third component can orient itself aroundthe metal-containing particles toform micellar colloidal particles.Accordingly, it can exist in the disperse system as an individual liquidcomponent dissolved in the disperse medium or it can be associated withthe metal-containing particles as a component of micellar colloidalparticles.

The following examples illustrate various overbased materials, andcolloidal disperse systems prepared from these overbased 'materials.Unless otherwise indicated, percentages and parts refer to percent byweight and parts by weight. The term naphtha. as used in the follow ingexamples refers to petroleum distillates boiling in the 1 7 range ofabout 90 C. to about 150 C. and usually designated Varnish Makers andPainters Naphtha.

Example 1 To a mixture of 3,245 grams (12.5 equivalents) of a mineraloil solution of barium petroleum sulfonate (sulfate ash of 7.6%), 32.5parts of octylphenol, 197 parts of Water, there is added 73 parts ofbarium oxide within a period of 30 minutes at 57 84 C. The mixture isheated at 100 C. for one hour to remove substantially all water andblown with 75 parts of carbon dioxide at 133 to 170 C. within a periodof 3 hours. A mixture of 1,000 grams of the above carbonatedintermediate product, 121.8 parts of octylphenol, and 234 parts ofbarium hydroxide is heated at 100 C. and then at 150 C. for 1 hour. Themixture is then blown with carbon dioxide at 150 C. for 1 hour at a rateof 3 cubic feet per hour. The carbonated product is filtered and thefiltrate is found to have a sulfate ash content of 39.8% and a metalratio of 9.3.

Example 2 To a mixture of 3,245 grams (12.5 equivalents) of bariumpetroleum sulfonate, 1,460 grams (7.5 equivalents) of heptylphenol, and2,100 grams of water in 8,045 grams of mineral oil there is added at 180C. 7,400 grams (96.5 equivalents) of barium oxide. The addition ofbarium oxide causes the temperature to rise to 143 C. which temperatureis maintained until all the water has been distilled. The mixture isthen blown with carbon dioxide until it is substantially neutral. Theproduct is diluted with 5,695 grams of mineral oil and filtered. Thefiltrate is found to have a barium sulfate ash content of 30.5% and ametal ratio of 8.1. Another inert liquid such as benzene, toluene,heptene, etc., can be substituted for all or part of the mineral oil.

Example 3 A mixture of 1,285 grams (1.0 equivalent) of 40% bariumpetroleum sulfonate and 500 milliliters (12.5 equivalents) of methanolis stirred at 55-60 C. while 301 grams (3.9 equivalents) of barium oxideis added portionwise over a period of 1 hour. The mixture is stirred anadditional 2 hours at 45-55 C., then treated with carbon dioxide at55-65 C. for 2 hours. The resulting mixture is freed of methanol byheating to 150 C. The residue is filtered through a siliceous filteraid, the clear, brown filtrate analyzing as: sulfate ash, 33.2%;slightly acid; metal ratio, 4.7.

Example 4 A stirred mixture of 57 grams (0.4 equivalent) of nonylalcohol and 3.01 grams (3.9 equivalents) of barium oxide is heated at150-175 C. for an hour, then cooled to 80 C. whereupon 400 grams (12.5equivalents) of methanol is added. The resultant mixture is stirred at7075 C. for 30 minutes, then treated with 1,285 grams (1.0 equivalent)of 40% barium petroleum sulfonate. This mixture is stirred at refluxtemperature for an hour, then treated with carbon dioxide at 6070 C. for2 hours. The mixture is then heated to 160 C. at a pressure of 18millimeters of mercury and thereafter filtered. The filtrate is a clear,brown oily material having the following analysis: sulfate ash, 32.5%;neutralization number, nil; metal ratio, 4.7.

Example (a) To a mixture of 1,145 grams of a mineral oil solution of a40% solution of barium mahogany sulfonates (1.0 equivalent) and 100grams of methyl alcohol at 55 C., there is added 220 grams of bariumoxide while the mixture is being blown with carbon dioxide at a rate of2 to 3 cubic feet per hour. To this mixture there is added an additional78 grams of methyl alcohol and then 460 grams of barium oxide while themixture is blown with carbon dioxide. The carbonated product is heatedto 150 C. for 1 hour and filtered. The filtrate is found to have a 18barium sulfate ash content of 53.8% and a metal ratio of 8.9.

(b) A carbonated basic metal salt is prepared in accordance with theprocedure of (a) except that a total of 16 equivalents of barium oxideis used per equivalent of the barium mahogany sulfonate. The productpossesses a metal ratio of 13.4.

Example 6 A mixture of 520 parts (by weight) of a mineral oil, 480 partsof a sodium petroleum sulfonate (molecular Weight of 480), and 84 partsof water is heated at 100 C. for 4 hours. The mixture is then heatedwith 86 parts of a 76% aqueous solution of calcium chloride and 72 partsof lime (90% purity) at C. for 2 hours, dehydrated by heating to a watercontent of less than 0.5%, cooled to 50 C., mixed with parts of methylalcohol, and then blown with carbon dioxide at 50 C. until substantiallyneutral. The mixture is then heated to C. to remove the methyl alcoholand water and the resulting oil solution of the basic calcium sulfonatefiltered. The filtrate is found to have a calcium sulfate ash content of16% and a metal ratio of 2.5.

A mixture of 1,305 grams of the above carbonated calcium sulfonate, 930grams of mineral oil, 220 grams of methyl alcohol, 72 grams of isobutylalcohol, and 38 grams of primary amyl alcohol is prepared, heated to 35C., and subjected to the following operating cycle 4 times: mixing with143 grams of 90% calcium hydroxide and treating the mixture with carbondioxide until it has a base number of 32-39. The resulting product isthen heated to C. during a period of 9 hours to remove the alcohols andfiltered through a siliceous filter aid at this temperature. Thefiltrate has a calcium sulfate ash content of 39.5% and a metal ratio of12.2.

Example 7 A basic metal salt is prepared by the procedure described inExample 6 except that the slightly basic calcium sulfonate having ametal ratio of 2.5 is replaced with a mixture of that calcium sulfonate(280 parts by weight) and tall oil acid (970 parts by weight having anequivalent weight of 340) and that the total amount of calcium hydroxideused is 930 parts by weight. The resulting highly basic metal salt ofthe process has a calcium sulfate ash content of 48%, a metal ratio of7.7, and an oil content of 31%.

Example 8 A highly basic metal salt is prepared by the procedure ofExample 7 except that the slightly basic calcium sulfonate startingmaterial having a metal ratio of 2.5 is replaced with tall oil acids(1,250 parts by weight, having an equivalent weight of 340) and thetotal amount of calcium hydroxide used is 772 parts by weight. Theresulting highly basic metal salt has a metal ratio of 5.2, a calciumsulfate ash content of 41%, and an oil content of 33%.

Example 9 A normal calcium mahogany sulfonate is prepared by metathesisof a 60% oil solution of sodium mahogany sulfonate (750 parts by weight)with a solution of 67 parts of calcium chloride and 63 parts of water.The reaction mass is heated for 4 hours at 90 to 100 C. to effect theconversion of the sodium mahogany sulfonate to calcium mahoganysulfonate. Then 54 parts of lime is added and the whole is heated to 150C. over a period of 5 hours. When the whole has cooled to 40 C., 98parts of methanol is added and 152 parts of carbon dioxide is introducedover a period of 20 hours at 4243 C. Water and alcohol are then removedby heating the mass to 150 C. The residue in the reaction vessel isdiluted with 100 parts of low viscosity mineral oil. The filtered oilsolution of the desired carbonated calcium sulfonate overbased materialshows the following analysis: sulfate ash content, 16.4%; neutralizationnumber, 0.6 (acidic); and

19 a metal ratio of 2.50. By adding barium or calcium oxide or hydroxideto this product with subsequent carbonation, the metal ratio can beincreased to a ratio of 3.5 or greater as desired.

Example 10 A mixture of 880 grams (0.968 mole) of a 57.5% oil solutionof the calcium sulfonate of tridecylbenzene bottoms (the bottomsconstitute a mixture of mono-, di-, and tridecylbenzene), 149 grams ofmethanol, and 59 grams (1.58 equivalents) of calcium hydroxide areintroduced into a reaction vessel and stirred vigorously. The whole isheated to 40-45 C. and carbon dioxide is introduced for 0.5 hour at therate of 2 cubic feet per hour. The carbonated reaction mixture is thenheated to 150 C. to remove alcohol and any water present, and theresidue is filtered for purposes of purification. The product, a 61% oilsolution of the desired overbased carbonated calcium sulfonate materialshows the following analysis: ash content, 16.8%; neutralization number,7.0 (acidic); and metal ratio, 2.42. By further carbonation in thepresence of an alkali or alkaline earth metal oxide, hydroxide, oralkoxide, the metal ratio can readily be increased to 3.5 or greater.

Example 11 A mixture of 2,090 grams (2.0 equivalents) of a 45% oilsolution of calcium mahogany sulfonate containing 1% of water, 74 grams(2.0 equivalents) of calcium hydroxide, and 251 grams of ethylene glycolis heated for 1 hour at 100 C. Carbon dioxide is then bubbled throughthe mixture at 4045 C. for 5.5 hours. The ethylene glycol and any waterpresent are removed by heating the mixture to a temperature of 185 C. at10.2 millimeters of mercury. The residue is filtered yielding thedesired overbased calcium sulfonate material, having the followinganalysis: sulfate ash, 12.9%; neutralization number 5.0 (acidic); and ametal ratio of 2.0 which can be increased to 3.5 or greater as desiredby carbonation in the presence of calcium oxide or hydroxide.

Example 12 A mixture comprising 1,595 parts of the overbased material ofExample 9 (1.54 equivalents based on sulfonic acid anion), 167 parts ofthe calcium phenate prepared as indicated below (0.19 equivalent), 616parts of mineral oil, 157 parts of 91% calcium hydroxide (3.86equivalents), 288 parts of methanol, 88 parts of isobutanol, and 56parts of mixed isomeric primary-amyl alcohols (containing about 65%normal amyl, 3% isoamyl and 32% of Z-methyl-l-butyl alcohols) is stirredvigorously at 40 C. and 25 parts of carbon dioxide is introduced over aperiod of 2 hours at 40-50 C. Thereafter, three additional portions ofcalcium hydroxide, each amounting to 1.57 parts, are added and each suchaddition is followed by the introduction of carbon dioxide as previouslyillustrated. After the fourth calcium hydroxide addition and thecarbonation step is completed, the reaction mass is carbonated for anadditional hour at 43-47 C. to reduce neutralization number of the massto 4.0 (basic). The substantially neutral, carbonated reaction mixtureis freed from alcohol and any water of reaction by heating to 150 C. andsimultaneously blowing it with nitrogen. The residue in the reactionvessel is filtered. The filtrate, an oil solution of the desiredsubstantially neutral, carbonated calcium sulfonate overbased materialof high metal ratio, shows the following analysis: sulfate ash content,41.11%; neutralization number 0.9 (basic); and a metal ratio of 12.55.

i The calcium phenate used above is prepared by adding 2,250 parts ofmineral oil, 960 parts (5 moles) of heptylphenol, and 50 parts of waterinto a reaction vessel and stirring at 25 C. The mixture is heated to 40C. and 7 parts of calcium hydroxide and 231 parts (7 moles) of 91%commercial paraformaldehyde is added over a period of 1 hour. The wholeis heated to 80 C. and 200 additional parts of calcium hydroxide (makinga total of 207 parts or 5 moles) is added over a period of 1 hour at -90C. The whole is heated to 150 C. and maintained at that temperature for12 hours while nitrogen is blown through the mixture to assist in theremoval of water. If foaming is encountered, a few drops of polymerizeddimethyl silicone foam inhibitor may be added to control the foaming.The reaction mass is then filtered. The filtrate, a 33.6% oil solutionof the desired calcium phenate of heptylphenol-formaldehyde condensationproduct is found to contain 7.56% sulfate ash.

Example 13 A mixture of 574 grams (0.5 equivalent) of 40% bariumpetroleum sulfonate, 98 grams (1.0 equivalent) of furfuryl alcohol, and762 grams of mineral oil is heated with stirring at 100 C. for an hour,then treated portionwise over a 15-minute period with 230 grams (3.0equivalents) of barium oxide. During this latter period, the temperaturerises to C. (because of the exothermic nature of the reaction of bariumoxide and the alcohol). The mixture then is heated to ISO- C. for anhour, and treated subsequently at this temperature for 1.5 hours withcarbon dioxide. The material is concentrated by heating to a temperatureof 150 C. at a pressure of 10 millimeters of mercury and thereafterfiltered to yield a clear, oil-soluble filtrate having the followinganalysis: sulfate ash content, 21.4%; neutralization number, 2.6(basic); and a metal ratio of 6.1.

Example 14 An overbased material is prepared by the procedure of Example6 except that the slightly basic calcium sulfonate starting material hasa metal ratio of 1.6 and the amount of this calcium sulfonate used is1,050 parts (by weight) and that the total amount of lime used is 630parts. The resulting metal salt has a calcium sulfate ash content of40%, a ratio of the inorganic metal group to the bivalent bridging groupof 16, and an oil content of 35% Example 15 To a mixture of 1,614 parts(3 equivalents) of a polyisobutenyl succinic anhydride (prepared by thereaction of a chlorinated polyisobutene having an average chlorinecontent of 4.3% and an average of 67 carbon atoms with maleic anhydrideat about 200 C.), 4,313 parts of mineral oil, 345 parts (1.8equivalents) of heptylphenol, and 200 parts of water, at 80 0., there isadded 1,038 parts (24.7 equivalents) of lithium hydroxide monohydrateover a period of 0.75 hour while heating to 105 C. Isooctanol (75 parts)is added while the mixture is heated to 150 C. over a 1.5-hour period.The mixture is maintained at ISO- C. and blown with carbon dioxide atrate of 4 cubic feet per hour for 3.5 hours. The reaction mixture isfiltered through a filter aid and the filtrate is the desired producthaving a sulfate ash content of 18.9% and a metal ratio of 8.0.

Example 16 The procedure of Example 6 is repeated except that anequivalent amount of sodium hydroxide is used in lieu of the calciumoxide. The product is the corresponding sodium overbased material.

Example 17 A mixture of 244 parts (0.87 equivalent) of maleic acid,parts of primary isooctanol, and 400 parts of mineral oil is heated to70 C. whereupon 172.6 parts (2.7 equivalents) of cadmium oxide is added.The mixture is heated for 3 hours at a temperature of 150 to 160 C.while removing water. Barium hydroxide monohydrate (324 parts, 3.39equivalents) is then added to the mixture over a period of 1 hour whilecontinuing to remove water by means of a side-arm water trap. Carbondioxide is blown through the mixture at a temperature of from 150 l60 C.until the mixture is slightly acidic to phenolphthalein.

21 Upon completion of the carbonation, the mixture is stripped to atemperature of 150 C. at 35 mm. of mercury to remove substantially allthe remaining water and alcohol. The residue is the desired overbasedproduct containing both barium and cadmium metal.

Example 18 The procedure of Example 13 is repeated except that thebarium sulfonate is replaced by an equivalent amount of potassiumsulfonate, and potassium oxide is used in lieu of the barium oxideresulting in the preparation of the corresponding potassium overbasedmaterial.

Example 19 A sulfoxide is prepared by treating polyisobutylene (averagemolecular weight 750) with 47.5% of its weight of SCl for 4.5 hours at220 C. A mixture of 787 grams (1.0 equivalent) of this sulfoxide, 124grams (0.6 equivalent) of diisobutylphenol, 550 grams of mineral oil,and 200 grams of water was warmed to 70 C. and treated with 360 grams(4.0 equivalents) of barium oxide. This mixture is heated at refluxtemperature for 1 hour and treated at 150 C. with carbon dioxide untilthe mixture is substantially neutral and thereafter filtered to yield aclear, oil-soluble liquid having the following analysis: sulfate ash,22.8%; neutralization number, 5.8 (basic); and metal ratio, 5.8.

Example 20 To a mixture of 268 grams (1.0 equivalent) of oleyl alcohol,675 grams of mineral oil, 124 grams (0.6 equivalent) ofdiisobutylphenol, and 146 grams of water, at 70 C. there is added 308grams (4.0 equivalents) of barium oxide. This mixture is heated atreflux temperature for 1 hour, then at 150 C. while bubbling carbondioxide therethrough until substantial neutrality of the mixture isachieved. The resulting reaction mass is filtered resulting in a clear,brown, oil-soluble filtrate having the following analysis: sulfate sashcontent, 29.8%; neutralization number 2.6 (basic); and metal ratio, 6.0.

Example 21 To a mixture of 423 grams (1.0 equivalent) of sperm oil, 124grams (0.6 equivalent) of heptylphenol, 500 grams of mineral oil, and150 grams of water there are added at 70 C. 308 grams (4.0 equivalents)of barium oxide. This mixture is heated at reflux temperature for 1hour, dried by heating at about 150 C. and thereafter carbonated bytreatment with carbon dioxide at the same temperature until the reactionmass was slightly acidic. Filtration yields a clear, light brown,non-viscous overbased liquid material having the following analysis:sulfate ash content, 32.0%; neutralization number 0.5 (basic); metalratio, 6.5.

To a mixture of 174 grams (1.0 equivalent) of N-octa- Example 22 decylpropylene diamine, 124 grams (0.6 equivalent) of diisobutylphenol, 766grams of mineral oil, 146 grams of water, there are added 306 grams (4.0equivalents) of barium oxide and the whole is refluxed for an hour.Water is subsequently removed by raising the temperature to 150 C. andthereafter carbon dioxide is bubbled there through while maintainingthis temperature. When the reaction mass is substantially neutral,carbon dioxide addition is ceased and the reaction mass filteredproducing a clear, oil-soluble liquid having the following analysis:sulfate ash content, 28.9%; neutralization number, 2.5 (basic); metalratio, 5.8.

Example 23 A mixture of 6,000 grams of a solution of barium petroleumsulfonate (sulfate ash 7.6% 348 grams of para-tertiary butylphenol, and2911 grams of water are heated to a temperature 60 C. while slowlyadding 1100 grams of barium oxide and raising the temperature to 94- 98C. The temperature is held within this range for about 1 hour and thenslowly raised over a period of 7 /2 hours to C. and held at this levelfor an additional hour assuring substantial removal of all water. Theresulting overbased material is a brown liquid having the followinganalysis: Sulfate ash content, 26.0%; metal ratio, 4.35.

This product is then treated with S0 until 327 grams of the masscombined with the overbased material. The product thus obtained has aneutralization number of zero. The SO -treated material was liquid andbrown in color.

One thousand grams of the SO -treated overbased material producedaccording to the preceding paragraph is mixed with 286 grams of waterand heated to a temperature of about 60 C. Subsequently, 107.5 grams ofbarium oxide are added slowly and the temperature is maintained at 94-98C. for 1 hour. Then the total reaction mass is heated to 150 C. over a1% hour period and held there for a period of 1 hour. The resultingoverbased material is purified by filtration, the filtrate being thebrown, liquid overbased material having the following analysis: sulfateash content, 33.7%; basic number, 38.6; metal ratio, 6.3.

Example 24 (a) A polyisobutylene having a molecular weight of 700-800 isprepared by the aluminum chloride-catalyzed polymerization ofisobutylene at 0-30 C., is nitrated with a 10% excess (1.1 moles) of 70%aqueous nitric acid at 70-75 C. for 4 hours. The volatile components ofthe product mixture are removed by heating to 75 C. at a pressure of 75mm. of mercury. To a mixture of 151 grams (0.19 equivalent) of thisnitrated polyisobutylene, 113 grams (0.6 equivalent) of heptylphenol,155 grams of water, and 2,057 grams of mineral oil there is added at 70C. 612 grams (8 equivalents) of barium oxide. This mixture is heated at150 C. for an hour, then treated with carbon dioxide at this sametemperature until the mixture is neutral (phenolphthalein indicator;ASTM D97453T procedure at 25 C.; a measurement of the degree ofconversion of the metal reactant, i.e., barium oxide, bicarbonation).The product mixture is filtered and the filtrate found to have thefollowing analysis: sulfate ash content, 27.6%; percent N, 0.06; andmetal ratio, 9.

(b) A mixture of 611 grams (0.75 mole) of nitrated polyisobutylene ofExample 1, 96 grams (0.045 mole) of heptylphenol, 2104 grams of mineraloil, 188 grams of water and 736 grams (4.8 moles) of barium oxide washeated at reflux temperature for an hour. The water was vaporized andcarbon dioxide passed into the mixture at 150 C. until the mixture wasno longer basic. This carbonated mixture was filtered and the clearfluid filtrate showed the following analysis: Sulfate ash content,26.3%; percent N, 0.15; base No. 2.4; metal ratio, 6.7.

Example 25 (a) A mixture of 1 equivalent of a nitrated polypropylenehaving a molecular weight of about 3,000, 2 equivalents of cetyl phenol,mineral oil, and 3 equivalents of barium hydroxide is heated at refluxtemperature for 1 hour. The temperature is then raised to 150 C. andcarbon dioxide is bubbled through the mixture at this temperature. Thereaction product is filtered and the filtrate is the desired overbasedmaterial.

(b) A solvent-refined, acid-treated Pennsylvania petroleum lubricatingoil is nitrated by treatment with 1.5 moles of 70% aqueous nitric acidat 5478 C. for 8 hours. After removal of volatile components of theproduct mixture by heating at 103 C. at a pressure of 15 mm. of mercuryfor 2 hours, a 787 gram portion 1.0 equivalent) of the nitrated productis treated with 2 grams (0.3 equivalent) of heptylphenol, 495 grams ofmineral oil, 90 grams of water, and 378 grams (5 equivalents) of bariumoxide. This mixture is heated at reflux temperature for an hour, thenfreed of water by distillation. The tem- 23 perature is increased to 150C. whereupon carbon dioxide is bubbled into the mixture until it isneutral. Filtration yields a clear filtrate with the following analysis:percent sulfate ash, 27.6; percent N, 0.5; and metal ratio, 3.1.

Example 26 (a) A mixture of 1,000 parts of mineral oil, 2 equivalents ofbarium hydride, 1 equivalent of 1-nitro-3-octadecyl-cyclohexane and 1equivalent (i.e., 0.5 mole) of 4,4'-methylene-bis(heptylphenol) iscarbonated at 100- 150 C. for 4 hours until the reaction mixture issubstantially neutral to phenolphthalein indicator. The reaction mass isfiltered and the desired product is the filtrate.

(b) A mixture of 1,000 parts of mineral oil, 3 equivalents of lithiumhydroxide, 1 equivalent of nitrated polyisobutene (prepared by mixing500 parts by weight of polyisobutene having an average molecular weightof 1,000 and 62.5 parts of 67% aqueous nitric acid at 65- 70 C. for 11hours) and para-butylphenol (1 equivalent) is carbonated according tothe technique of (a) above to produce the corresponding lithiumoverbased material.

Example 27 A copolymer of isobutene and piperylene (weight ratio of98.2) having a molecular weight of about 2,000, is nitrated by theprocedure used in the preceding example for the nitration ofpolyisobutene. An overbased product is then prepared from this nitratedreactant by mixing 1 equivalent thereof with 1 equivalent ofu-butyl-B-naphthol and 7 equivalents barium hydroxide, diluting themixture with mineral oil to a 50% oil mixture, and then carbonating themixture at 120-l60 C. until it is substantially neutral tophenolphthalein indicator. The reaction product is filtered and thefiltrate is the desired overbased product.

Example 28 A mixture of 630 grams (2 equivalents) of a rosin amine(consisting essentially of dehydroabietyl amine) having a nitrogencontent of 44% and 245 grams (1.2 equivalents) of heptylphenol having ahydroxyl content of 8.3% is heated to 90 C. and thereafter mixed with230 grams (3 equivalents) of barium oxide at 90140 C. The mixture ispurged with nitrogen at 140 C. A 600 gram portion is diluted with 400grams of mineral oil and filtered. The filtrate is blown with carbondioxide, diluted with benzene, heated to remove the benzene, mixed withxylene, and filtered. The filtrate, a xylene solution of the product hasa barium sulfate ash content of 25.1%, a nitrogen content of 2%, and areflux base number of 119. (The basicity of the metal composition isexpressed in terms of milligrams of KOH which are equivalent to one gramof the composition.) For convenience, the basicity thus determined isreferred to in the specification as a reflux base number.

Example 29 An amine-aldehyde condensation product is obtained asfollows: formaldehyde (420 grams, 4 moles) is added in small incrementsto a mixture comprising N-octadecylpropylenediamine (1,392 grams, 4moles), mineral oil (300 grams), water (200 grams), and calciumhydroxide (42 grams-condensation catalyst) at the reflux temperature,i.e., 100-105 C. The rate of addition of formaldehyde is such as toavoid excessive foaming. The mixture is heated at reflux temperature for1 hour, slowly heated to 155 C., and blown with nitrogen at 150-155 C.for 2 hours to remove all volatile components. It is then filtered. Thefiltrate, 93% of the theoretical yield, is a 65.4% oil solution of theamine-aldehyde condensation product having a nitrogen content of 2.4%.

A 1,850 gram portion (3.2 equivalents of nitrogen) is mixed with 1,850grams of heptylphenol (0.97 equivalents), 1,485 grams of mineral oil,and 1,060 grams of 90% pure barium oxide (12.6 equivalents) and heatedto 70 C. Over a period of 1 hour, 500 grams of water is 24 added whilemaintaining the temperature in the range of 70100 C. The mixture isheated'at' 110 to 15 C. for 4.7 hoursand thereafter to 150 vC. Whilemaintaining the temperature within the range of 140-150 C., the,reaction mixture is carbonated and subsequently filtered. The filtrateis a 57.8% oil solution of the overbased amine-aldehyde condensationproduct having a nitrogen content of 0.87% and a barium sulfate ashcontent of 29.5%.

Example 30 A partially acylated polyamine reactant is prepared asfollows: a mixture (565 parts by weight) of an akylene amine mixtureconsisting of triethylene tetramine and diethylene triamine in Weightratio of 3:1 is added at 20- C. to a mixture of naphthenic acid havingan acid number of 180 (1,270 parts) and oleic acid (1,110 parts). Thetotal quantity of the two acids used is such as to provide 1 equivalentof acid for each two equivalents of the amine mixture used. The reactionis exothermic. The mixture is blown with nitrogen while it is beingheated to 240 C. in 4.5 hours and thereafter heated at this temperaturefor 2 hours. Water is collected as the distillate.

To the above residue, ethylene oxide (140 parts) is added at 170-180 C.within a period of 2 hours while nitrogen is bubbled through thereaction mixture. Nitrogen blowing is continued for an additional 15minutes and the reaction mixture then diluted with 940 parts of xyleneto a solution containing 25% by weight of xylene to a solutioncontaining 25 by weight of xylene. The resulting solution has a nitrogencontent of 5.4% and a base number of 82 at pH of 4, the latter beingindicative of free amino groups.

A 789 gram portion of the above xylene solution (3 equivalents ofnitrogen) is heated to 150 C. at a pressure of 2 millimeters of mercuryto distill off xylene and is then mixed with 367 grams of heptylphenol(having a hydroxyl content of 8.3%; 1.8 equivalents). To this mixturethere is added 345 grams (4.5 equivalents) of barium oxide in smallincrements at 111 C. The mixture is heated at 90-120 C. for 2.5 hoursand blown with carbon dioxide for 1.75 hours. It is diluted with gramsof xylene and then heated at C. for 3.5 hours. It is then diluted with20% by weight of xylene and filtered. The filtrate has a barium sulfateash content of 33.2%, a nitrogen content of 3.52% and a reflux basenumber of 134.

Example 31 To a mixture of 408 grams (2 equivalents) of heptylphenolhaving a hydroxyl content of 8.3% and 264 grams of xylene there is added383 grams (5 equivalents) of barium oxide in small increments at 85 -110C. Thereafter, 6 grams of water is added and the mixture is carbonatedat 100-130 C. and filtered. The filtrate is heated to 100 C. dilutedwith xylene to a 25 xylene solution. This solution has a barium sulfateash content of 41% and a reflux base number of 137.

Example 32 A mixture of 5846 parts (4.0 equivalents) of a neutralcalcium sulfonate having a calcium sulfate ash content of 4.68% (66%mineral oil), 464 parts (2.4 equivalents) of heptylphenol, and 3.4 partsof water is heated to 80 C. whereupon 1,480 parts (19.2 equivalents) ofbarium oxide is added over a period of 0.6 hour. The reaction isexothermic and the temperature of the reaction mixture reaches 100 C.The mixture is heated to 150 C. and carbonated at this temperature.During the carbonation, 24 parts of barium chloride were added to themixture. Oil was removed from the reaction mixture during thecarbonation procedure. Carbonation is continued at this temperatureuntil the mixture has a base number (phenolphthalein) of 80. Octylalcohol (164 parts) and a filter aid are added to the mixture and themixture 25 is filtered while hot. The filtrate is the desired overbasedbarium bright stock sulfonate havinga barium sulfate ash content of26.42, a metal ratio of 4.6 and a reflux base number of 104.

Example 33 Following the procedure for preparing barium and calciumoverbased sulfonates exemplified above, sodium mahogany sulfonate (0.26equivalent), 1 equivalent of phenol, and 5.3 equivalents of strontiumoxide are carbonated until the reaction mixture is almost neutral. Theresulting overbased material is filtered, the filtrate being the desiredproduct and having a metal ratio of 4.6.

Example 34 A barium overbased carboxylic acid is prepared by carbonatinga mixture of 9.8 equivalents of barium hydroxide, 1 equivalent ofheptylphenol, and 0.81 equivalent of a polyisobutene substitutedsuccinic anhydride wherein the polyisobutenyl portion thereof has anaverage molecular weight of 1,000.

Example 35 A mixture of 1,000 parts by weight of a polyisobutene havinga molecular weight of 1,000 and 90 parts of phosphorus pentasulfide isprepared at room temperature, heated to 260 C. over hours, andmaintained at this temperature for an additional 5 hours. The reactionmass is then cooled to 106 C. and hydrolyzed by treatment with steam atthis temperature for 5 hours. The hydrolyzed acid has a phosphoruscontent of 2.4%, a sulfur content of 2.8%. In a separate vessel, amixture of oil and barium hydroxide is prepared by mixing 2,200 parts ofa mineral oil and 1150 parts of barium oxide at 88 C. and blowing themixture with steam for 3 hours at 150 C. To this mixture there is addedportionwise throughout a period of 3 hours, 1,060 parts of the abovehydrolyzed acid while maintaining the temperature at 145 -150 C., andthen 360 parts of heptylphenol is added over a 1.5 hour period. Theresulting mixture is blown with carbon dioxide at the rate of 100 partsper hour for 3 hours at 150-157 C. The carbonated product is mixed with850 parts of a mineral oil and dried by blowing it with nitrogen at atemperature of 150 C. The dry product is filtered and the filtrate isdiluted with mineral oil to a solution having a barium sulfate ashcontent of 25%. The final solution has a phosphorus content of 0.38%, asulfur content of 0.48%, a neutralization number less than 5 (basic), areflux base number of 109, and a metal ratio of 7.2.

Example 36 (a) To a mixture of 268 grams (1.0 equivalent) of oleylalcohol, 124 grams (0.6 equivalent) of heptylphenol, 988 grams ofmineral oil, and 160 grams of water there is added 168 grams (4.0equivalents) of lithium hydroxide monohydrate. The mixture is heated atreflux temperature for an hour and then carbonated at 150 C. until it issubstantially neutral. The filtration of this carbonated mixture yieldsa liquid having a lithium sulfate content of 12.7%.

(b) To a mixture of 1,614 parts (3 equivalents) of a polyisobutenylsuccinic anhydride prepared by the reaction of a chlorinatedpolyisobutene having an average chlorine content of 4.3% and an averageof 67 carbon atoms with maleic anhydride at about 200 C., 4,313 parts ofmineral oil, 345 parts (1.8 equivalents) of heptylphenol, and 200 partsof water, at 80 C., there is added 1,038 parts (24.7 equivalents) oflithium hydroxide monohydrate over a period of 0.75 hour while heatingto 105 C. Isooctanol (75 parts) is added while the mixture is heated to150 C. in about 1.5 hours. The mixture is maintained at 150-170 C. andblown with carbon dioxide at the rate of 4 cubic feet per hour for 3.5hours. The reac tion mixture is filtered through a'filter aid and thefiltrate is the desired product having a sulfate ash content of 18.9 anda metal ratio of 8.

Example 37 A thiophosphorus acid is prepared as set forth in Example 35above. A mixture of 890 grams of this acid (0.89 equivalent), 2,945grams of mineral oil, 445 grams of heptylphenol (2.32 equivalents), and874 grams of lithium hydroxide monohydrate (20.8 equivalents) formed byadding the metal base to the mineral oil solution of the acid and theheptylphenol over a 1.5 hour period maintaining the temperature at 110C. and thereafter drying at C. for 2 hours, carbon dioxide is bubbledtherethrough at the rate of 4 cubic feet per hour until the reactionmixture was slightly acidic to phenolphthalein, about 3.5 hours, whilemaintaining the temperature within the range of 150-160 C. The reactionmixture is then filtered twice through a diatomaceous earth filter. Thefiltrate is the desired lithium overbased thio-phosphorus acid materialhaving a metal ratio of 6.3.

Example 38 (a) A reaction mixture comprising 2,442 grams (2.8equivalents) of strontium petrosulfonate, 3,117 grams of mineral oil,150 grams of isooctanol, and 910 grams of methanol is heated to 55 C.and thereafter 615 grams of strontium oxide (11.95 equivalents) is addedover a 10 minute period while maintaining the reaction at a temperatureof 55-65 C. The mixture is heated an additional hour at this sametemperature range and thereafter blown with carbon dioxide at a rate of4 cubic feet per hour for about 3 hours until the reaction mixture wasslightly acidic to phenolphthalein. Thereafter the reaction mixture isheated to C. and held there for about 1 hour while blowing the nitrogenat 5 cubic feet per hour. Thereafter, the product is filtered, thefiltrate being the desired overbased material having a metal ratio of3.8.

(b) To a mixture of 3,800 parts (4 equivalents) of a 50% mineral oilsolution of lithium petroleum sulfonate (sulfate ash of 6.27%), 460parts (2.4 equivalents) of heptylphenol, 1,920 parts of mineral oil, and300 parts of Water, there is added at 70 C. 1,216 parts (28.9equivalents) of lithium hydroxide monohydrate over a period of 0.25hour. This mixture is stirred at 110 C. for 1 hour, heated to 150 C.over a 2.5 hour period, and blown with carbon dioxide at the rate of 4cubic feet per hour over a period of about 3.5 hours until the reactionmixture is substantially neutral. The mixture is filtered and thefiltrate is the desired product having a sulfate ash content of 25.23and a metal ratio of 7.2.

Example 39 A mixture of alkylated benzene sulfonic acids and naphtha isprepared by adding 1,000 grams of a mineral oil solution of the acidcontaining 18% by weight mineral oil (1.44 equivalents of acid) and 222grams of naphtha. While stirring the mixture, 3 grams of calciumchloride dissolved in 90 grams of water and 53 grams of Mississippi lime(calcium hydroxide) is added. This mixture is heated to 97-99 C. andheld at this temperature for 0.5 hour. Then 80 grams of Mississippi limeare added to the reaction mixture with stirring and nitrogen gas isbubbled therethrough to remove water, while heating to 150 C. over a 3hour period. The reaction mixture is then cooled to 50 C. and grams ofmethanol are added. The resulting mixture is blown with carbon dioxideat the rate of 2 cubic feet per hour until substantially neutral. Thecarbon dioxide blowing is discontinued and the water and methanolstripped from the reaction mixture by heating and bubbling nitrogen gastherethrough. While heating to remove the water and methanol, thetemperature rose to 146 C. over a 1.75 hour period. At this point themetal ratio of the overbased material was 2.5 and the product is aclear, dark viscous liquid. This material is permitted to cool to 50 C.and thereafter 1256 grams thereof is mixed with 574 grams of naphtha,222 grams of methanol, 496 grams of Mississippi lime, and 111 grams ofan equal molar mixture of isobutanol and amyl alcohol. The mixture isthoroughly stirred and carbon dioxide is blown therethrough at the rateof 2 cubic feet per hour for 0.5 hour. An additional 124 grams ofMississlppi lime is added to the mixture with stirring and the COblowing continued. Two additional 124 gram increments of Mississippilime are added to the reaction mixturewhile continuing the carbonation.Upon the addition of the last increment, carbon dioxide is bubbledthrough the mixture for an additional hour. Thereafter, the reactronmixture is gradually heated to about 146 C. over a 3.25 hour periodwhile blowing with nitrogen to remove water and methanol from themixture. Thereafter, the mixture is permitted to cool to roomtemperature and filtered producing 1,895 grams of the desired overbasedmaterial having a metal ratio of 11.3. The material contams 6.8% mineraloil, 4.18% of the isobutanol-amyl alcohol and 30.1% naphtha.

Example 40 A mixture of 406 grams of naphtha and 214 grams of amylalcohol is placed in a three-liter flask equipped with reflux condenser,gas inlet tubes, and stirrer. The mixture 15 stirred rapidly whileheating to 38 C. and adding 27 grams of barium oxide. Then 27 grams ofWater are added slowly and the temperature rises to 45 C. Stirring ismaintained while slowly adding over 0.25 hour 73 grams of oleic acid.The mixture is heated to 95 C. with continued mixing. Heating isdiscontinued and 523 grams of barium oxide are slowly added to themixture. The temperature rises to about 115 C. and the mixture ispermitted to cool to 90 C. whereupon 67 grams of water are slowly addedto the mixture and the temperature rises to 107 C. The mixture is thenheated within the range of 107-120 C. to remove water over a 3.3 hourperiod while bubbling nitrogen through the mass. Subsequently, 427 gramsof oleic acid is added over a 1.3 hour period while maintaining atemperature of 120-125 C. Thereafter heating is terminated and 236 gramsof naphtha is added. Carbonation is commenced by bubbling carbon dioxidethrough the mass at two cubic feet per hour for 1.5 hours during whichthe temperature is held at 8117 C. The mixture is heated under anitrogen purge to remove water. The reaction mixture is filtered twiceproducing a filtrate analyzing as follows: sulfate ash content, 34.42%;metal ratio, 3.3. The filtrate contains 10.7% amyl alcohol and 32%naphtha.

Example 41 A reaction mixture comprising 1,800 grams of a calciumoverbased petrosulfonic acid containing 21.7% by weight mineral oil,36.14% by weight naphtha, 426 grams naphtha, 225 grams of methanol, and127 grams of an equal molar amount of isobutanol and amyl alcohol areheated to 45 C. under reflux conditions and 148 grams of Mississippilime (commercial calcium hydroxide) is added thereto. The reaction massis then blown with carbon dioxide at the rate of 2 cubic feet per hourand thereafter 148 grams of additional Mississippi lime added.Carbonation is continued for another hour at the same rate. Twoadditional 147 gram increments of Mississippi lime are added to thereaction mixture, each increment followed by about a 1 hour carbonationprocess. Thereafter, the reaction mass is heated to a temperature of 138C. while bubbling nitrogen therethrough to remove water and methanol.After filtration, 2,220 grams of a solution of the barium overbasedpetrosulfonic acid is obtained having a metal ratio of 12.2 andcontaining 12.5% by weight mineral oil, 34.15% by weight naphtha, and4.03% by weight of the isobutanol amyl alcohol mixture.

Example 42 r (a) Following the procedure of Example 2 above, thecorresponding lead product is prepared by replacing the bariumpetrosulfonate with lead petroleum sulfonate (1 equivalent) and bariumoxide with lead oxide (25 equivalents) Example 43 (a) A mixturecomprising 280 parts of a commercial mixture of fatty acids distilledfrom tall oil acids (sold as Acintol FA-l Special by the ArizonaChemical Company and said to comprise about 44% linoleic acids, 52%oleic acids, and 4% saturated carboxylic acids), 1,123 parts of VM and Pnaphtha (Varnish Makers and Painters naphtha), 148 parts calciumhydroxide, and 67 parts methanol is carbonated at 50-55 C. until thecarbon dioxide uptake substantially ceases, that is, until the amount ofcarbon dioxide introduced into the mixture is substantially equal to theamount of carbon dioxide exiting the mixture. The carbonated mass isblown with nitrogen while the temperature is elevated to about 117 C.over a 1.75 hour period and thereafter filtered. The filtrate is aclear, dark amber liquid characterized by a sulfate ash content of about14.5% and a metal ratio of about 3.3.

(b) A mixture comprising 282 parts of the carboxylic acid mixturedescribed in (a), 876 parts boiled linseed oil, 175 parts methanol, 44parts primary amyl alcohol, and 296 parts of calcium hydroxide iscarbonated for about three hours while maintaining a temperature of 7779C. at which time the carbon dioxide uptake has substantially ceased andthe carbonated mass has a neutralization number (phenophthalein) ofabout 1.6 (basic). This carbonated mixture is blown with nitrogen forone hour while the temperature is elevated to 150 C. and is then held atabout 150 C. for an additional hour with continued nitrogen blowing atwhich time 383 parts of xylene are added. The mixture containing xyleneis held at about 10 C. for about 025 hour and filtered. The filtrate isa clear, dark amber solution of the desired carbonated,calcium-overbased carboxylic acid mixture (metal ratio of about 7.7)containing about 46% linseed oil and 20% xylene. It is characterized bya calcium sulfate ash content of about 27.5%.

(c) A mixture comprising 280 parts of the carboxylic acid mixture of(a), 1271 parts VM and P naphtha, 272 parts calcium hydroxide, and 140parts methanol, is carbonated for about 0.75 hour at a temperature of60- 65 C. Then 272 parts of calcium hydroxide are added and carbonationis continued for about 1.3 hours at 60- 65 C. at which point the carbondioxide uptake has substantially ceased. The carbonated mixture is thenblown with nitrogen while heating at 120 C. to remove water andmethanol. It is then filtered at a temperature of about 115 C. Thefiltrate is a 60% naphtha solution of the desired carbonated,calcium-overbased carboxylic acid mixture (metal ratio about 9.9) and ischaracterized by a calcium sulfate ash content of 31.7%.

Following the general procedure of (c) above, a carbonated,calcium-overbased carboxylic acid mixture as described in (a) and havinga metal ratio of about 14.5 is prepared as a clear, golden orangefiltrate containing about 50% naphtha and characterized by a calciumsulfate ash content of about 45.6%. The process involves firstneutralizing the carboxylic acids with a stoichiometrically equivalentamount of calcium hydroxide and then adding with carbonation twoincrements of calcium hydroxide, each providing about seven equivalentsof calcium for each equivalent of acid.

Example 44 (a) A mixture of 520 parts mineral oil, 480 parts of a sodiumsalt of an alkylated benzene sulfonic acid (average molecular Weight480), and 84 parts of water is heated at about 100 C. for four hours.The mixture is then heated with 86 parts of a 76% aqueous solution ofcalcium chloride and 72 parts of lime (90% purity) at C. for two hours,dehydrated by heating to a Water content or less than 0.5%, cooled to 50C., mixed with 130 parts of methyl alcohol, and then blown with carbondioxide at 50 C. until substantially neutral. The resulting mixture isheated to 150 C. to remove methyl alcohol and water and the resultingoil solution of the basic calcium sulfonate filtered. The filtrate ischaracterized by a calcium sulfate ash content of 16% and a metal ratioof about 2.5. A mixture of 1305 parts of this filtrate, 930 parts ofmineral oil, 220 parts of methyl alcohol, 72 parts of isobutyl alcohol,and 38 parts of amyl alcohol is heated to 35 C. and subjected to thefollowing procedure four times: mixing with 143 parts of lime (90%calcium hydroxide) and treating the mixture with carbon dioxide until ithas a base number of 3239. The resulting carbonated mixture is heated to155 C. during a period of nine hours to remove the alcohol andsubsequently filtered. The filtrate is a mineral oil solution of thedesired carbonated, calcium-overbased sulfonic acid salt (metal ratioabout 12.2) characterized by a calcium sulfate ash content of about39.5%.

(b) A carbonated, calcium-overbased metal salt is prepared according tothe general procedure of Example 2(a) except that the slightly basiccalcium sulfonate having a metal ratio of 2.5 is replaced with a mixtureof that calcium sulfonate (280 parts weight) and tall oil acids (970parts having an equivalent weight of 340) and the total amount ofcalcium hydroxide used is 930 parts. The filtrate is characterized by acalcium sulfate ash content of 48%, and an oil content of 31%. Thecarbonated, calcium-overbased acid salt mixture has a metal ratio ofabout 7.7.

(c) A carbonated, calcium-overbased organic acid salt prepared accordingto the general procedure of Example 2(a) except that the slightly basiccalcium sulfonate starting material having a metal ratio of 2.5 isreplaced with tall oil acids (1,250 parts having an equivalent weight of340), and the total amount of calcium hydroxide is 772 parts. The acidsalt thus produced has a metal ratio of 5.2. The filtrate ischaracterized by a calcium sulfate ash content of about 41% and an oilcontent of about 33%.

(d) A carbonated, calcium-overbased salt is prepared by the generalprocedure of Example 2(a) except that the slightly basic calciumsulfonate starting material is replaced with a mixture of that basiccalcium sulfonate (555 parts) and tall oil acids (694 parts having anequivalent weight of 340) and the amount of calcium hydroxide used is772 parts. The filtrate is a mineral oil solution of the desiredoverbased salt having a metal ratio of about 7.9 and is furthercharacterized by sulfate ash content of about 45% and an oil content ofabout 32%.

The above examples illustrate various means for preparing overbasedmaterials suitable for conversion to the non-Newtonian colloidaldisperse systems utilized in the present invention. Obviously, it iswithin the skill of the art to vary these examples to produce anydesired overbased material. Thus, other acidic materials such asmentioned hereinbefore can be substituted for the CO S and acetic acidused in the above examples. Similarly, other metal bases can be employedin lieu of the metal base used in any given example. Or mixtures ofbases and/ or mixtures of materials which can be overbased can beutilized. Similarly, the amount of mineral oil or other non-polar,inert, organic liquid used as the overbasing medium can be varied widelyboth during overbasing and in the overbased product.

The following examples illustrate the conversion of the Newtonianoverbased materials into non-Newtonian colloidal disperse systems byhomogenization with conversion agents.

Example I To 733 grams of the overbased materials of Example 5(a) thereis added 179 grams of acetic acid and 275 grams of a mineral oil (havinga viscosity of 2,000 SUS at 100 F.) at 90 C. in 1.5 hours with vigorousagitation. The mixture is then homogenized at 150 C. for 2 hours 30 andthe resulting material is the desired colloidal disperse system.

Example II A mixture of 960 grams of the overbased material of Example 5(b), 256 grams of acetic acid, and 300 grams of a mineral oil (having aviscosity of 2000 SUS at F.) is homogenized by vigorous stirring at 150C. for 2 hours. The resulting product is a non-Newtonian colloidaldisperse system of the type contemplated for use by the presentinvention.

The overbased materials of Examples I and II can be converted withoutthe addition of additional mineral oil or if another inert organicliquid is substituted for the mineral oil.

Example III A mixture of 150 parts of the overbased material of Example6, 15 parts of methyl alcohol, 10.5 parts of amyl alcohol, and 45 partsof water is heated under reflux conditions at 7174 C. for 13 hourswhereupon the mixture gels. The gel is heated for 6 hours at 144 C.,diluted with 126 parts of the mineral oil of the type used in Example Iabove the diluted mixture heated to 144 C. for an additional 4.5 hours.The resulting thickened product is a colloidal disperse system. Again,it is not necessary that the material be diluted with mineral oil inorder to be useful. The gel itself which results from the initialhomogenization of the overbased material and the lower alkanol mixtureis a particularly useful colloidal disperse system for incorporatinginto resinous compositions.

Example IV A mixture of 1000 grams of the product of Example 12, 80grams of methanol, 40 grams of mixed primary amyl alcohols (containingabout 65% by weight of normal amyl alcohol, 3% by weight of isoamylalcohol, and 32% of 2-methyl-l-butyl alcohol) and 80 grams of water areintroduced into a reaction vessel and heated to 70 C. and maintained atthat temperature for 4.2 hours. The overbased material is converted to agelatinous mass, the latter is stirred and heated at 150 C. for a periodof about 2 hours to remove substantially all the alcohols and water. Theresidue is a dark green, gel which is a particularly useful colloidaldisperse system.

Example V The procedure of Example IV is repeated except that grams ofwater is used to replace the water-alkanol mixture employed as theconversion agent therein. Conversion of the Newtonian overbased materialinto the non-Newtonian colloidal disperse system requires about 5 hoursof homogenization. The disperse system is in the form of a gel.

Example VI To 600 parts by weight of the overbased material of Example6, there is added 300 parts of dioctylphthalate, 48 parts of methanol,36 parts of isopropyl alcohol, and 36 parts of Water. The mixture isheated to 7077 C". and maintained at this temperature for 4 hours duringwhich the mixture becomes more viscous. The viscous solution is thenblown with carbon dioxide for 1 hour until substantially neutral tophenolphthalein. The alcohols and water are removed by heating toapproximately C. The residue is the desired colloidal disperse system.

Example VII To 800 parts of the overbased material of Example 6, thereis added 300 parts of kerosene, 120 parts of an alcohol: water mixturecomprising 64 parts of methanol, 32 parts of water and 32 parts of theprimary amyl alcohol mixture of Example IV. The mixture is heated to 75C. and maintained at this temperature for 2 hours during which time theviscosity of the mixture increases. The

31 water and alcohols are removed by heating the mixture to about 150 C.while blowing with nitrogen for '1 hour. The residue is the desiredcolloidal disperse system having the consistency of a gel.

Example VIII A mixture of 340 parts of the product of Example 6, 68parts of an alcoholzwater solution consisting of 27.2 parts of methanol,20.4 parts of isopropyl alcohol and 20.4 parts of water, and 170 partsof heptane is heated to 65 C. During this period, the viscosity of themixture increases from an initial value of 6,250 to 54,000.

The thickened colloidal disperse system is further neutralized byblowing the carbon dioxide at the rate of lbs. per hour for 1 hour. Theresulting mass is found to have a neutralization number of 0.87 (acid tophenolphthalein indicator).

Example IX The procedure of Example VIII is repeated except that thecalcium overbased material of Example 6 is replaced by an equivalentamount of the cadmium and barium overbased material of 'Example 17.Xylene (200 parts) is used in lieu of the heptane and the furthercarbonation step is omitted.

Example X A mixture of 500 parts of the overbased material of Example 6,312 parts of kerosene, 40 parts of methylethyl ketone, 20 parts ofisopropyl alcohol, and 50 parts of water is prepared and heated to 75 C.The mixture is maintaned at a temperature of 70-75 C. for 5 hours andthen heated to 150 C. to remove the volatile components. The mixture isthereafter blown with ammonia for 30 minutes to remove most of the finaltraces of volatile materials and thereafter permitted to cool to roomtemperature. The residue is a brownish-tan colloidal disperse system inthe form of a gel.

Example XI A mixture of 500 parts of the product of Example 6, 312 partsof kerosene, 40 parts of acetone, and 60 parts of water is heated toreflux and maintained at this temperature for 5 hours with stirring. Thetemperature of the material is then raised to about 155 C. whileremoving the volatile components. The residue is a viscous gel-likematerial which is the desired colloidal disperse system.

Example XII The procedure of Example XI is repeated with thesubstitution of 312 parts of heptane for the kerosene and 60 parts ofWater for the acetone-water mixture therein. At the completion of thehomogenization, hydrogen gas is bubbled through the gel to facilitatethe removal of water and any other volatile components.

Example XIII To 500 parts of the overbased material of Example 9, thereis added 312 parts of kerosene, 40 parts of o-cresol, and 50 parts ofwater. This mixture is heated to the reflux temperature (7075 C.) andmaintained at this temperature for 5 hours. The volatile components arethen removed from the mixture by heating to 150 C. over a period of 2hours. The residue is the desired colloidal disperse system containingabout 16% by weight of kerosene.

Example XIV A mixture of 500 parts of the overbased material of Example5(a) and 312 parts of heptane is heated to 80 C. whereupon 149 parts ofglacial acetic acid (99.8% by weight) is added dropwise over a period of5 hours. The mixture is then heated to 150 C. to remove the volatilecomponents. The resulting gel-like material is the desired colloidaldisperse system.

Example XV The procedure of Example XIV is repeated except that 232parts of boric acid is used in lieu of the acetic acid. The desired gelis produced.

Example XVI The procedure of Example XII is repeated except that thewater is replaced by 40 parts of methanol and 40 parts of diethylenetriamine. Upon completion of the homogenization, a gel-like colloidaldisperse system is produced.

Example XVII A mixture of 500 parts of the product of Example 6 and 300parts of heptane is heated to C. and 68 parts of anthranilic acid isadded over a period of 1 hour while maintaining the reaction temperaturebetween 80 and C. The reaction mixture is then heated to C. over a 2hour period and blown with nitrogen for 15 minutes to remove thevolatile components. The resulting colloidal disperse system is amoderately stiff gel.

Example XVIII The procedure of Example XVII is repeated except that theanthranilic acid is replaced by 87 parts of adipic acid. The resultingproduct is very viscous and is the desired colloidal disperse system.This gel can be diluted, if desired, with mineral oil or any of theother materials said to be suitable for disperse mediums hereinabove.

Example XIX Example XX A mixture of 300 parts of toluene and 500 partsof an overbased material prepared according to the procedure of Example7 and having a sulfate ash content of 41.8% is heated to 80 C. whereupon124 parts of glacial acetic acid is added over a period of 1 hour. Themixture is then heated to C. to remove the volatile components. Duringthis heating, the reaction mixture becomes very viscous and 380 parts ofmineral oil is added to facilitate the removal of the volatilecomponents. The resulting colloidal disperse system is a very viscousgreaselike material.

Example XXI A mixture of 700 parts of the overbased material of Example5 b), 70 parts of water, and 350 parts of toluene is heated to refluxand blown with carbon dioxide at the rate of 1 cubic foot per hour for 1hour. The reaction product is a soft gel.

Example XXII The procedure of Example XVIII is repeated except that theadipic acid is replaced by 450 grams of di(4-methyl-amyl)phosphorodithioic acid. The resulting material is a gel.

Example XXIII The procedure of Example XVI is repeated except that themethanol-amine mixture is replaced by 250 parts of a phosphorus acidobtained by treating with steam at 150 C. the product obtained byreacting 1,000 parts of polyisobutene having a molecular weight of about60,000, with 24 parts of phosphorus pentasulfide. The product is aviscous brown gel-like colloidal disperse system.

33 Example XXIV The procedure of Example XX is repeated except that theoverbased material therein is replaced by an equivalent amount of thepotassium overbased material of Example 18 and the heptane is replacedby an equivalent amount of toluene.

Example XXV The overbased material of Example 6 is isolated as a drypowder by precipitation out of a benzene solution through the additionthereto of acetone. The precipitate is Washed with acetone and dried.

A mixture of 45 parts of a toluene solution of the above powder (364parts of toluene added to 500 parts of the powder to produce a solutionhaving a sulfate ash content of 43%), 36 parts of methanol, 27 parts ofwater, and 18 parts of mixed isomeric primary amyl alcohols (describedin Example IV) is heated to a temperature within the range of 70-75 C.The mixture is maintained at this temperature for 2.5 hours and thenheated to remove the alkanols. The resulting material is a colloidaldisperse system substantially free from any mineral oil. If desired, thetoluene present in the colloidal disperse system as the disperse mediumcan be removed by first diluting the disperse system with mineral oiland thereafter heating the diluted mixture to a temperature of about 160C. whereupon the toluene is vaporized.

Example XXVI Calcium overbased material similar to that prepared inExample '6 is made by substituting xylene for the mineral oil usedtherein. The resulting overbased material has a xylene content of about25% and a sulfate ash content of 39.3%. This overbased material isconverted to a colloidal disperse system by homogenizing 100 parts ofthe overbased material with 8 parts of methanol, 4 parts of the amylalcohol mixture of Example IV, and 6 parts of water. The reaction massis mixed for 6 hours while maintaining the temperature at 75 78 C.Thereafter, the disperse system is heated to remove the alkanols andwater. If desired, the gel can be diluted by the addition of mineraloil, toluene, xylene, or any other suitable disperse medium.

Example XXVII Air at the rate of 5 cubic feet per hour is blown throughan overbased material of the type prepared according to Example 6 havinga calcium sulfonate ash content of 44.1% while rapidly stirring it at205 C. for 24 hours. The product, on cooling is a gel having a calciumsulfate ash content of 48.14% and a reflux base number of 368.

Example XXVIII A colloidal disperse system of the type prepared inExample XXVII is obtained following the same technique and blowing withair for 28 hours at a temperature of 190 C.

Example XXIX A solution of 1,000 grams of the gel-like colloidaldisperse system of Example III is dissolved in 1,000 grams of toluene bycontinuous agitation of these two components for about 3 hours. Amixture of 1,000 grams of the resulting solution, 20 grams of water, and20 grams of methanol are added to a 3-liter flask. Thereafter, 92.5grams of calcium hydroxide is slowly added to the flask with stirring.An exothermic reaction takes place raising the temperature to 32 C. Theentire reaction mass is then heated to about 60 C. over a 0.25 hourperiod. The heated mass is then blown with carbon dioxide at the rate of3 standard cubic feet per hour for 1 hour while maintaining thetemperature at 60-70 C. At the conclusion of the carbonation, the massis heated to about 150 C. over a 0.75 hour period to remove water,methan01, and toluene. The resulting product is a clear, light browncolloidal disperse system in the form of a gel. In this manneradditional metal containing particles are incorporated into thecolloidal disperse system.

At the conclusion of the carbonation step and prior to removing thewater, methanol, and toluene, more calcium hydroxide could have beenadded to the mixture and the carbonation step repeated in order to addstill additional metal-containing particles to the colloidal dispersesystem.

Example XXX A mixture of 1200 grams of the gel produced according toExample III, 600 grams of toluene, and 48 grams of water is blown withcarbon dioxide at 2 standard cubic feet per hour while maintaining thetemperature at 55- 65 C. for 1 hour. The carbonated reaction mass isthen heated at 150 C. for 1.75 hours to remove the water and toluene.This procedure improves the texture of the colloidal disperse systemsand converts any calcium oxide or calcium hydroxide present in the gelproduced according to Example III into calcium carbonate particles.

Example XXXI A mixture comprising 300 grams of water, 70 grams of theamyl alcohol mixture identified in Example IV above, 100 grams ofmethanol, and 1,000 grams of a barium overbased oleic acid, preparedaccording to the general technique of Example 3 by substituting oleicacid for the petrosulfonic acid used therein, and having a metal ratioof about 3.5 is thoroughly mixed for about 2.5 hours while maintainingthe temperature within the range of from about 72-74 C. At this pointthe resulting colloidal disperse system was in the form of a very softgel. This material was then heated to about 150 C. for a 2 hour periodto expel methanol, the amyl alcohols, and water. Upon removal of theseliquids, the colloidal disperse system was a moderately stiff, gel-likematerial.

Example XXXII A dark brown colloidal disperse system in the form of avery stiff gel was prepared from the product of Example 39 using amixture of 64 grams of methanol and grams of water as the conversionagent to convert 800 grams of the overbased material. After theconversion process, the resulting disperse system is heated to about 150C. to remove the alcohol and water.

Example XXXIII 1,000 grams of the overbased material of Example 40 isconverted to a colloidal disperse system by using as a conversion agenta mixture of grams of methanol and 300 grams of water. The mixture isstirred for 7 hours at a temperature within the range of 72-80 C. At theconclusion of the mixing, the resulting mass is heated gradually to atemperature of about C. over a 3 hour period to remove all volatileliquid contained therein. Upon removal of all volatile solvents, a tanpowder was obtained. By thoroughly mixing this tan powder to a suitableorganic liquid such as naphtha, it is again transformed into a colloidaldisperse system.

Example XXXIV A mixture of 1000 grams of the product of Example 41, 100grams of water, 80 grams of methanol, and 300 grams of naphtha weremixed and heated to 72 C. under reflux conditions for about 5 hours. Alight brown viscous liquid material is formed which is the desiredcolloidal disperse system. This liquid is removed and consists of thecolloidal disperse system wherein about 11.8% of the disperse medium ismineral oil and 88% is naphtha.

Following the techniques of Example III additional overbased materialsas indicated below are converted to the corresponding colloidal dispersesystems.

Overbased material converted Example No.: to colloidal disperse systemXXXV Example 15 XXXVI Example 21 XXXVII Example 23 XXXVIII Example 24(a)XXXIX Example 28 XL Example 31 XLI Example 39 XLII Example 40 ExampleXLIII (a) A mixture comprising 80 parts water, 60 parts methanol, and 60parts isopropanol is added to 1,000 parts of a filtrate preparedaccording to the general procedure of Example 2(a) and the resultingmixture is heated to reflux (about 77 C.) over a 0.5 hour period. Thismaterial is then refluxed for one hour at this temperature with vigorousmechanical stirring. At the completion of this homogenization step, theproduct is a gel. Approximately half of the gel is then stripped byheating and stirring at 160 C. for 1.75 hours producing a very stiffdark brown gel. The remaining portion was stripped several days later byheating at 150 C. for 1.25 hours. There is no apparent differences inthe two gels.

(b) Five hundred parts of a homogenized calciumoverbased sulfonic acidsalt prepared according to the general procedure of Example XLIII(a), in250 parts toluene and 20 parts water is carbonated for about 0.75 hour.The carbonated product is then heated to 145 C. over a two-hour periodto strip water and toluene from the product. The stripped product ischaracterized by a neutralization number (phenophthalein) of less thanone (acid).

(c) The general procedure of Example XLIII(b) is repeated except thatsulfur dioxide is used in lieu of carbon dioxide. After stripping iscompleted, the sulfur dioxide blown homogenized product is an opaque,yellowish brown viscous liquid characterized by a sulfur content of5.48% and a calcium sulfate ash content of 39.67%.

(d) A homogenized, carbonated, calcium-overbased sulfonic acid isprepared according to the general procedure of Example 2(a) except thatthe mineral oil is replaced with VM and P naphtha. 1000 parts of thehomogenized product thus produced, 540 parts additional parts VM and Pnaphtha, 100 parts water and 100 parts methanol is thoroughly mixedwhile heating at about 75 C. for 3 hours during which time the materialbecomes lighter in color, somewhat opaque, and thickens. This thickenedproduct is then blown with carbon dioxide for 0.5 hour while thetemperature is maintained at about 58-75 C. At the end of thiscarbonation, the gel has a neutralization number (phenophthalein) ofless than one (acid). Thereafter, the material is stripped by heatingfrom 58 C. to 115 C. over 1.6 hours while blowing with nitrogen duringwhich time 199 parts of water and alcohol are removed.

Example XLIV (a) A homogenized product prepared according to the generalprocedure of Example 3(a) is diluted with an equivalent weight of lowviscosity mineral oil. Thereafter 2,500 parts of this dilutedhomogenized product, 232 parts calcium hydroxide, 50 parts water, 50parts methanol, and 1,250 parts toluene is carbonated while maintaininga temperature of 50-55 C. for 1.5 hours at which time the carbon dioxideuptake has substantially ceased. Thereafter, 942 parts additional lowviscosity mineral oil is added and the resulting material is blown withnitrogen gas while heating from 50 C. to 120 C. over a twohour period.The mass is then stripped to 160 C. and a pressure of 20 mm. (Hg) over1.8 hours. The product is a brown viscous liquid characterized by acalcium sulfate ash content of 24.91% and a mineral oil content of 75%.This corresponds to a total metal ratio of 24.

(b) A mixture comprising 750 parts of a homogenized product producedaccording to the general procedure of Example 3(a), 333 parts of calciumhydroxide, 38 parts of low viscosity mineral oil, 25 parts water, 65parts methanol, and 1,000 parts toluene is carbonated while maintaininga temperature of about 45 -50 C. for 3.75 hours at which time the carbondioxide uptake has substantially ceased. The carbonated mass is thenstripped to a temperature of 150 C. over a two-hour period. Theresulting material is a very stiff tan gel, characterized by a calciumsulfate ash content of 73.95% and a total mineral oil content of about33%. This corresponds to a metal ratio of 36.

(c) A mixture comprising 200 parts of a homogenized product producedaccording to the general procedure described in Example 3(a), 1,100parts low viscosity mineral oil, 222 parts of calcium hydroxide, partsof toluene, 20 parts water, and 50 parts methanol, is carbonated whilemaintaining a temperature of S'055 C. for 2.75 hours during which timean additional 20 parts water, 100 parts toluene and 50 parts methanolare added. Carbonation is continued at this same temperature for anadditional three hours. Thereafter, the carbonated mass is dried byblowing with nitrogen while heating from 50 C. to 160 C. over 1.25hours. The product is a beige liquid characterized by a sulfate ashcontent of 30.1% and contains a total of about 75% low viscosity mineraloil. This corresponds to a metal ratio of about 78.

Example XLV A mixture comprising 2,000 parts of a carbonated,calcium-overbased sulfonic acid prepared according to the generalprocedure of Example 2(a) wherein VM and P naphtha was substituted forthe mineral oil, 193 parts of mineral oil, 160 parts water, partsmethanol, 120 parts isopropanol, and 307 parts additional VM and Pnaphtha is heated at reflux for about two hours while thoroughly mixingwith a mechanical mixing device. The material becomes ligher and verythick. Then, 693 parts of VM and P naphtha is added and the resultingmass is blown with carbon dioxide for about 0.5 hour during which timethe homogenized product becomes substantially neutral. The carbonatedmass is then stripped to a temperature of 100 C. and a pressure of 1 mm.(Hg) over a 1.5 hour period to produce a thick, dark brown gelcharacterized by a calcium sulfate ash content of 54%.

Example XLVI A mixture comprising 1,000 parts of a carbonated,calcium-overbased sulfonic acid prepared according to the generalprocedure of Example 2(a) where VM and P naphtha is substituted formineral oil, 500 parts additional VM and P naphtha. parts water, and 150parts of methanol are vigorously mixed while maintaining the refluxtemperature for a period of about 2.5 hours. This homogenizationprocedure causes the material to gel. The gel is then blown with carbondioxide for about 0.5 hour until it is substantially neutral. Aftercarbonation, the gel is heated from 75 C. to 110 C. over three hourswhile blowing with nitrogen during which time 300 parts of water andmethanol are removed. The gelled material is then stripped to atemperature of 100 C. and a pressure of 1 mm. (Hg) to remove 350 partsof VM and P naphtha. The resulting product is a clear brown gel.

The preparation of other non-Newtonian colloidal disperse systems usefulin the compositions of this invention are disclosed in copendingapplications Ser. No. 535,048 filed Mar. 17, 1966, and Ser. No. 535,693filed Mar. 21, 1966.

The change in rheological properties associated with conversion of aNewtonian overbased material into a non-Newtonian colloidal dispersesystem is demonstrated by the Brookfield viscometer data derived fromoverbased materials and colloidal disperse systems prepared therefrom.In the following samples, the overbased material and the colloidaldisperse systems are prepared according to the above-discused andexemplified techniques. In each case, after preparation of the overbasedmaterial and the colloidal disperse system, each is blended withdioctylphthalate (DOP) so that the compositions tested in the viscometercontains 33.3% by weight DOP (Samples A, B, and C) or 50% by weight DOP(Sample D). In Samples A-C, the acidic material used in prepared theoverbased material is carbon dioxide while in Sample D, acetic acid isused. The samples each are identified by two numbers, (1) and (2). Thefirst is the overbased material-DOP composition and the second thecolloidal disperse systemDOP composition. The overbased materials of thesamples are further characterized as follows:

SAMPLE A Calcium overbased petrosulfonic acid having a metal ratio ofabout 12.2.

SAMPLE B Barium overbased oleic acid having a metal ratio of about 3.5.

SAMPLE C Barium overbased petrosulfonic acid having a metal ratio ofabout 2.5.

SAMPLE D Calcium overbased commercial higher fatty acid mixture having ametal ratio of about 5.

The Brookfield Viscometer data for these compositions is tabulatedbelow. The data of all samples is collected at 25 C.

TABLE.BROOKFIELD VISCOMETER DATA IN After the homogenization step, thehomogenized product is suitable for preparing the solid,metal-containing compositions of this invention. It has been foundadvantageous to subject the homogenized product to a posttreatmentwhereby an acidic gas such as CO S or H S, is blown through thehomogenized product to reduce the residual basicity thereof. A methodfor achieving this neutralization is described in my US. Pat. 3,422,013.

To prepare the desired solid, metal-containing compositions, themetal-containing materials produced in the homogenization step must beseparated from the nonpolar, inert organic diluents. This separationstep can be acheived by thin-film evaporation techniques, vacuumdistillaton procedures, precipitation techniques, and the like asdescribed hereinafter.

Precipitation of the desired solid, metal-containing compositions isreadily accomplished by admixing the homogenized product With asubstantially inert, polar, organic liquid diluent. Upon mixing of thesematerials, the solid, metal-containing material precipitates and can berecovered, if desired, from the polar phase by filtration, decantation,dialysis, evaporation of the liquid, and the like. When the solid,metal-containing compositions are recovered by the precipitationprocedure, they usually exist as dry powders after removal of the polarorganic liquid used to precipitate them. However, when the organicdiluent is removed directly by evaporation of the liquid portion of thehomogenized product, the solid, metal-containing compositions tend tocake or form solids which may be powdered easily by conventionalpowdermaking techniques such as grinding, ball-milling, etc.

If evaporation techniques such as thin-film evaporation procedures areutilized to separate the solid, metal-containing compositions from theorganic liquid present in the homogenized products, the temperatureshould not be permitted to exceed about 350 (3., preferably 300 C., inorder to avoid thermal decomposition of the desired product. Ifevaporation procedures are used to achieve separation, the use ofreduced pressures may be necessary to avoid exceeding these temperatureswhere the diluent is not readily removed at lower temperatures.

The substantially, inert, polar organic liquids utilized in separatingthe solid, metal-containing compositions from the nonpolar diluents bythe precipitation technique are not critical and any polar organicliquid may be employed for this purpose as long as it does, in fact,cause the metal-containing compositions to precipitate. It is preferredthat these polar diluents have boiling points at standard temperatureand pressure less than 300 C. for the reason stated above, i.e., toavoid thermal decomposition if the polar liquid is removed bydistillation, evaporation, etc. In fact, it is convenient to selectpolar organic liquids boiling at lower temperatures, e.g., less than C.,since this facilitates subsequent drying of the precipitate if thatshould be desired. It is sometimes convenient to use the polar organicliquids in admixture with nonpolar diluents such as describedhereinbefore (e.g., hexane, octane, benzene, etc.) to facilitate mixing,etc. For reasons of economy, availability, ease of use, and excellentresults achieved, aliphatic alcohols and ketones constitute a preferredgroup of polar organic liquids for precipitating the solid,metal-containing compositions with the lower alkanols and lower alkylketones, either symmetrical or unsymmetrical, and mixtures thereof beingespecially preferred. Specific examples include methanol, ethanol,n-propanol, n-butanol, n-pentanol, nhexanol, n-heptanol, isopropylalcohol, isobutyl alcohol, tertiary butyl alcohol, isoamyl alcohol,tertiary amyl alcohol, allyl alcohol, 2-chloroethanol,1-chloro-2-propanol, dimethyl ketone, diethyl ketone, dipropyl ketone,dibutyl ketone, diamyl ketone, methyl ethyl ketone, methyl propylketone, methyl butyl ketone, methyl amyl ketone, methyl hexyl ketone,ethyl propyl ketone, chloroacetone, diacetone alcohol and the like.Alkyl ketones and alkanols of up to four carbon atoms each and mixturesthereof are particularly effective, e.g., acetone, isopropanol, andmixtures of these. Other organic liquids which can be used alone inadmixture with the alcohols or ketones include dimethylformamide,dimethylacetamide, carbon tetrachloride, trichloro benzenes, diethylether of ethylene glycol, diethyl ether, dioxane, and the like. Whilepentane is not a polar organic liquid, it also possesses the ability tocause most of the solid, metal-containing composition to precipitatefrom the homogenized products.

When employing the precipitation technique, the organic polar liquid andthe homogenized product are mixed in a weight ratio of polar liquid tohomogenized product of about 0.5:1 to 20:1. Better separation isachieved in most instances, however, if the minimum ratio is at leastabout 1.5 :1. Generally, there is no advantage in exceeding a ratio ofabout 10:1. Precipitation normally commences as soon as the polar liquidand homogenized products are mixed, even at ambient temperature. Coolingmay be employed to increase the efficiency of separation. Afterprecipitation, the precipitated solid, metal-containing compositions canbe recovered by filtration, centrifugation, and other conventionalmeans.

The following examples illustrate the separation processes of thepresent invention. The solid, metal-containing compositions produced bythese processes are illustrative of the products of this invention. Asused in these examples and elsewhere in the specification, percentagesand parts refer to percent by weight and parts by weight unlessotherwise specified.

Example A (a) Xylene is added to a post-carbonated homogenized productprepared according to the general procedure of Example XLIII(b) in anamount sufiicient to provide a weight ratio of homogenized product toxylene of 70:30. A mixture comprising 1,333 parts of the xylene dilutedhomogenized product, 667 parts toluene, 185 parts calcium hydroxide, 40parts methanol, and 40 parts Water is carbonated for two hours whilemaintaining a temperature of 50 C. to 70 C. At the end of this time, thecarbonated mixture is slightly acidic. The carbonated mixture is thenheated from 70 C. to 120 C. over a 2.5 hour period to remove water andmethanol. The resulting mixture is a pale brown liquid solution of thediluted homogenized calcium-over-based sulfonic acid salts which is nowcharacterized by a metal ratio of about 24.

(b) One hundred parts of the product of Example A(a) is added at roomtemperature to 200 parts of acetone. The desired solid,calcium-containing composition precipitates. After settling for 0.5hour, the liquid portion is decanted. Then an additional 100 parts ofacetone are added to the precipitate and again the whole is allowed tostand for 0.5 hour. The liquid is again decanted and an additional 100parts of xylene is added With stirring. The precipitate settles over a0.5 hour period and recovered by filtration. The solid filtered materialis dried in an oven for two hours producing a beige powder characterizedby a calcium carbonate content of 73.6%. Analysis of the acetonewashings establishes that there are 15.4 parts of oil in the first, 5.2parts in the second, and 2.8 in the third.

(c) Five hundred parts of the product produced according to Example A(a)is added to 1,000 parts of acetone at room temperature. The desiredsolid, calcium-containing composition precipitates and is filtered. Thefilter cake is then dissolved in 190 parts of 1,1,1-trichloroethane toproduce a dark brown opaque liquid which consists essentially of about36% of the desired precipitated micellar complex, 29% acetone, and 34%1,1,1-trichloroethane.

(d) Five hundred parts of the diluted product of Example A(a) is addedto 1,000 parts of acetone at room temperature. The desiredcalcium-containing composition precipitates and is recovered byfiltration and dried. The dried product is a beige powder containing1.47% sulfur, and 69.8% calcium carbonate.

Example B (a) A mixture comprising 500 parts of isopropanol and 1,500parts of a product prepared according to the general procedure ofExample XLIII(b) is heated to about 60 C. and added to a flaskcontaining 4,000 parts of isopropanol. A beige precipitate formsimmediately as the first formed mixture is added to the isopropanol. Theresulting mixture is stirred for about 0.25 hour and the liquid phase isdecanted. The precipitate is then dried in an oven for 72 hours at 130C. The product is a hard brown solid which can be easily reduced to apowder by ball milling or other types of grinding. The solid ischaracterized by a calcium sulfate ash content of 68.4%, a C content ofabout 18.6%, and a sulfur content of 2.18%.

(b) Five hundred parts of the homogenized product prepared according tothe general procedure of Example XLIII(b) is added to 1,500 parts ofisopropanol and mixed for 0.5 hour at room temperature. This mixture isthen centrifuged and the thus isolated calcium-containing compositionplaced in an oven and dried for three hours at 50 C. The resultingmaterial is the desired micellar complex in the form of a solid brownmaterial containing 23.8% calcium.

Example C (a) A post-carbonated homogenized product prepared accordingto the general procedure of Example XLIII(b) is diluted with xylene inan amount sutficient to provide a 70:30 weight ratio of homogenizedproduct to xylene. Subsequently, 2,500 parts of this mixture is added atroom temperature to a previously prepared mixture of 6,250 parts each ofacetone and isopropanol. The desired calcium-containing compositionprecipitates immediately and is allowed to settle over a two-hourperiod. Most of the liquid is removed from the precipitate bydecantation and the remainder is thereafter removed by drying in avacuum oven. The final product is a dark brown easily powdered solid.

(b) To a mixture comprising 2,100 parts each of acetone and isopropanolis added 1,066 parts of the diluted homogenized product described inExample C(a) above and mixed for about 0.75 hour. The precipitate whichforms is then allowed to settle and most of the liquid layer issubsequently removed by decantation. The precipitate is filteredproducing 530 parts of wet filter cake. Then 265 parts of the wet filtercake is dried in a vacuum oven producing 166 parts of dry material whichis pebblemilled to produce a fine, light-brown powder which is thedesired calcium-containing composition. The powder is characterized by acalcium content of 24.1% and a sulfur content of 2.2%.

The remaining half of the filter cake (containing about 37% liquidsolvent is mixed with 289 parts of 1,1,1-trichloroethane to produce a30% solution of the desired calcium-containing composition.

(c) A mixture comprising 500 parts of a homogenized material preparedaccording to the general procedure of Example XLIII(b) and 1,500 partsof acetone is mixed for 0.5 hour at room temperature during which time aprecipitate forms. The liquid layer is then removed by decantation and1,500 parts of isopropanol are added for an additional 0.5 hour. Againthe liquid layer is decanted and the precipitate is recovered byfiltration and thereafter dried by heating for three hours at 50 C. in avacuum. The product is a brown powder characterized by a calcium contentof 25.7%.

(d) A mixture comprising 2,000 parts of a homogenized product preparedaccording to the general procedure of Example XLIII(b) and 6,000 partsacetons is stirred for 0.5 hour at which time 2,000 additional parts ofacetone are added and stirring is continued for 0.25 hour. Most of theliquid layer is then removed by decantation and 6,000 parts ofisopropanol are thereafter added to the precipitate and mixed for 0.5hour. Again, the liquid layer is removed by decantation and theprecipitate recovered by filtration. The filtrate is dried in a vacuumoven at 50 C. and the dried material is ball-milled. The product is afine beige powder characterized by a sulfur content of 2.4% and acalcium content of 24.7%.

(e) To a mixture comprising 1,000 parts hexane and 4,000 parts ofacetone there is added 1,000 parts of a xylene-diluted post-carbonatedhomogenized product prepared according to the procedure of ExampleXLIII(b) (diluted with xylene to produce a weight ratio of homogenizedproduct to xylene of 70:30). This mixture is stirred for about tenminutes at room temperature and thereafter the precipitate which formedalmost immediately is allowed to settle for 0.5 hour. Then, 3,984 partsof liquid is removed by decantation, 2,000 parts acetone and 500 partshexane is added and mixed with the precipitate. After allowing theprecipitate to settle, 2,383 parts of liquid are decanted and 2,000parts of acetone, and 500 parts hexane are added to the precipitate.After stirring and settling, 2,849 parts of liquid are removed bydecantation. Then 800 parts of 1,1,1-trichloroethane are added to theprecipitate and the resulting mixture is heated on a waterbathmaintained at a temperature of about C. while blowing with nitrogen toproduce a clear, dark brown viscous liquid solution of the desiredcalcium-containing composition comprising about 51%1,1,1-trichloroethane and about 67% of a mixture of acetone and hexane.

